U.S. patent application number 10/484291 was filed with the patent office on 2004-12-16 for use of compounds in products for laundry applications.
Invention is credited to Blokzijl, Wilfried, Chang, Han Ting, Charmot, Dominique, Jayaraman, Manikandan, Jones, Christopher Clarkson, Mansky, Paul.
Application Number | 20040254089 10/484291 |
Document ID | / |
Family ID | 26246408 |
Filed Date | 2004-12-16 |
United States Patent
Application |
20040254089 |
Kind Code |
A1 |
Charmot, Dominique ; et
al. |
December 16, 2004 |
Use of compounds in products for laundry applications
Abstract
Laundry treatment products comprise a graft polymer benefit
agent and at least one additional laundry cleaning ingredient. The
graft polymer benefit agent preferably provides soil release or
fabric care benefits. The graft polymer benefit agent comprises a
polysaccharide backbone and a plurality of graft chains extending
from the backbone, each graft chain having a degree of
polymerisation between 5 and 250. The graft polymer is
substantially free of cross-linking and has a degree of
substitution of grafts across a bulk sample in the range of from
0.02 to 1.0. The graft polysaccharide copolymers may be prepared
using living-type free radical polymerisation techniques which
provide control over the degree of substitution, the graft/co-block
composition and structure.
Inventors: |
Charmot, Dominique;
(Campbell, CA) ; Jayaraman, Manikandan; (San
Francisco, CA) ; Chang, Han Ting; (Livermore, CA)
; Mansky, Paul; (San Francisco, CA) ; Blokzijl,
Wilfried; (Wirral, GB) ; Jones, Christopher
Clarkson; (Wirral, GB) |
Correspondence
Address: |
UNILEVER
PATENT DEPARTMENT
45 RIVER ROAD
EDGEWATER
NJ
07020
US
|
Family ID: |
26246408 |
Appl. No.: |
10/484291 |
Filed: |
August 2, 2004 |
PCT Filed: |
July 10, 2002 |
PCT NO: |
PCT/EP02/07685 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60306738 |
Jul 20, 2001 |
|
|
|
Current U.S.
Class: |
510/475 |
Current CPC
Class: |
C11D 3/3788
20130101 |
Class at
Publication: |
510/475 |
International
Class: |
C11D 003/37 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 7, 2001 |
GB |
0119258.2 |
Claims
1. A laundry cleaning composition comprising a graft polymer
benefit agent and at least one additional laundry cleaning
ingredient, the graft polymer benefit agent comprising a
polysaccharide backbone and a plurality of graft chains extending
from said backbone, each of said plurality of graft chains having a
degree of polymerisation between 5 and 250, wherein said graft
polymer is substantially free of cross-linking and has a degree of
substitution of grafts across a bulk sample in the range of from
0.02 to 1.0.
2. A composition according to claim 1, wherein said degree of
polymerisation is between 25 and 250 and the degree of substitution
of grafts across the bulk sample is in the range of from 0.02 to
0.2.
3. A composition according to claim 1, wherein the grafts on the
polysaccharide backbone have a degree of polymerisation of between
50 and 100.
4. A composition according to claim 1, wherein said degree of
polymerisation is between 5 and 50 and the degree of substitution
of grafts across the bulk sample is in the range of from 0.1 to
1.0
5. A composition according to claim 1, wherein the number of grafts
ranges from about 3 to 12 per polysaccharide backbone.
6. A composition according to claim 1, wherein said graft chains
are homopolymers.
7. A composition according to claim 1, wherein said graft chains
are copolymers.
8. A composition according to claim 1, wherein said polysaccharide
backbone is cellulose, a cellulose derivative, a xyloglucan, a
glucomannan, a galactomannan, chitosan or a chitosan salt.
9. A composition according to claim 1, wherein said polysaccharide
backbone has a number average molecular weight from about 10,000 to
about 40,000.
10. A composition according to claim 1, wherein said polymer is
water soluble at a concentration of at least about 0.2 mg/mL.
11. A composition according to claim 1, wherein the polymer
comprises a polysaccharide backbone and at least one pendant
polymeric chain attached to said polysaccharide backbone, wherein
said at least one chain comprises a control agent moiety that is
selected from the group consisting of 22where Z is selected from
the group consisting of optionally substituted alkyl, alkenyl,
alkynyl, aralkyl, alkaryl, heteroalkyl, heteroalkenyl,
heteroalkynyl, alkoxy, aryl, heteroaryl, amino; R" is selected from
the group consisting of optionally substituted hydrocarbyl and
heteroatom-containing hydrocarbyl, and the group is attached to a
linker or sugar unit via either the Z or R" groups; and
--O--NR.sup.5R.sup.6 wherein each of R.sup.5 and R.sup.6 is
independently selected from the group consisting of hydrocarbyl,
substituted hydrocarbyl, heteroatom containing hydrocarbyl and
substituted heteroatom containing hydrocarbyl; and optionally
R.sup.5 and R.sup.6 are joined together in a ring structure.
12. A composition according to claim 11, wherein on average there
are between 0.5 and 25 pendant polymeric chains attached to said
polysaccharide backbone.
13. A composition according to claim 1, wherein said grafts have a
number average molecular weight of from 100 to 10,000,000 Da.
14. A composition according to claim 1, wherein said polysaccharide
backbone has a number average molecular weight of from about 3,000
to about 100,000.
15. A composition according to claim 11, wherein said pendant
polymeric chains are attached to said polysaccharide backbone at a
site selected from the group consisting of a terminus of said
polysaccharide backbone and a mid-point of said polysaccharide
backbone and combinations thereof.
16. A composition according to claim 1, wherein the polymer has the
general formula I: 23wherein SU represents a sugar unit in a
polysaccharide, preferably cellulosic backbone, L is an optional
linker, Y is a control agent moiety as defined in claim 11, a is in
the range of from 3-80, b is in the range of from about 1-25, c is
0 or 1, and d is 1-3.
17. A composition according to claim 16, wherein c is 1 and said
linker L comprises 2 to 50 non-hydrogen, preferably carbon,
atoms.
18. A composition according to claim 17, wherein said linker is
selected from the group consisting of di-isocyanates, methanes, and
amides.
19. A composition according to claim 1 comprising from 0.01% to
25%, preferably from 0.05% to 15%, more preferably from 0.1 to 5%
by weight of said polymer.
20. A composition according to claim 1, wherein the at least one
additional ingredient is selected from surfactants, detergency
builders, bleaches, transition metal sequestrants, enzymes, fabric
softening and/or conditioning agents, lubricants for inhibition of
fibre damage and/or for colour care and/or for crease reduction
and/or for ease of ironing, UV absorbers such as fluorescers and
photofading inhibitors, for example sunscreens/UV inhibitors and/or
anti-oxidants, fungicides, insect repellents and/or insecticides,
perfumes, dye fixatives, waterproofing agents, deposition aids,
flocculants, anti-redeposition agents and soil release agents.
21. A method of delivering one or more laundry benefits in the
cleaning of a textile fabric, the method comprising contacting the
fabric with a polymer as defined in claim 1, preferably in the form
of a laundry cleaning composition comprising said polymer, and most
preferably in the form of an aqueous dispersion or solution of said
composition.
Description
FIELD OF INVENTION
[0001] The present invention relates to compounds (including
oligomers and polymers) which are useful in laundry treatment
products, e.g. for incorporation in products for dosing in the wash
and/or rinse. They are intended for, but not limited to, soil
release, fabric care and/or other laundry cleaning benefits in such
products.
BACKGROUND OF THE INVENTION
[0002] The compounds utilised by the present invention have been
found, dependent upon the structure of the compound in question, to
deliver a soil release, fabric care and/or other laundry cleaning
benefit.
[0003] The deposition of a benefit agent onto a substrate, such as
a fabric, is well known in the art. In laundry applications typical
"benefit agents" include fabric softeners and conditioners, soil
release polymers, sunscreens; and the like. Deposition of a benefit
agent is used, for example, in fabric treatment processes such as
fabric softening to impart desirable properties to the fabric
substrate.
[0004] Conventionally, the deposition of the benefit agent has had
to rely upon the attractive forces between the oppositely charged
substrate and the benefit agent. Typically this requires the
addition of benefit agents during the rinsing step of a treatment
process so as to avoid adverse effects from other charged chemical
species present in the treatment compositions. For example,
cationic fabric conditioners are incompatible with anionic
surfactants in laundry washing compositions.
[0005] Such adverse charge considerations can place severe
limitations upon the inclusion of benefit agents in compositions
where an active component thereof is of an opposite charge to that
of the benefit agent. For example, cotton is negatively charged and
thus requires a positively charged benefit agent in order for the
benefit agent to be substantive to the cotton, i.e. to have an
affinity for the cotton so as to absorb onto it. Often the
substantivity of the benefit agent is reduced and/or the deposition
rate of the material is reduced because of the presence of
incompatible charged species in the compositions. However, in
recent times, it has been proposed to deliver a benefit agent in a
form whereby it is substituted onto another chemical moiety which
increases its affinity for the substrate in question.
[0006] The compounds used by the present invention for soil-release
and/or other benefits are substituted polysaccharide structures,
especially substituted cellulosic structures.
[0007] Recently, substituted cellulosic oligomers and polymers have
been proposed as ingredients in laundry products for providing a
variety of different benefits such as fabric rebuild, as disclosed
in WO-A-98/29528, WO-A-99/14245, WO-A-00/18861, WO-A-/18862,
WO-A-00/40684 and WO-A-00/40685.
[0008] U.S. Pat. No. 4,235,735 discloses cellulose acetates with a
defined degree of substitution as anti-redeposition agents in
laundry products.
[0009] Cellulosic esters are also known for use in non-laundry
applications, as described in WO-A-91/16359 and GB-A-1 041 020.
[0010] The grafting of synthetic polymers onto a cellulosic
backbone has been the subject of research activities for a long
time with the object of producing a polymer that has the beneficial
properties of both cellulose and the synthetic polymers. Enormous
research and development efforts have occurred over the last 40
years, but no polymer or process has yet been discovered which has
proceeded to commercialisation.
[0011] The grafting of polymers on a cellulosic backbone proceeds
through radical polymerisation wherein an ethylenic monomer is
contacted with a soluble or insoluble cellulosic material together
with a free radical initiator. The radical thus formed reacts on
the cellulosic backbone (usually by proton abstraction), creates
radicals on the cellulosic chain, which subsequently react with
monomers to form graft chains on the cellulosic backbone. Related
techniques use other sources of radical such as high energy
irradiation or oxidising agents such as Cerium salt or redox
systems such as thiocarbonate-potassium bromate. These methods are
well known, see, e.g., McDonald, et al. Prog. Polym. Sci. 1984, 10,
1; Hebeish et al, "The Chemistry and Technology of cellulosic
copolymers", (Springer Verlag, 1981); Samal et al. J. Macromol.
Sci-Rev.Macromol. Chem. 1986, 26, 81; Waly et al, Polymers &
polymer composites 4,1,53,1996; and D. Klenn et al, Comprehensive
Cellulose Chemistry, vol. 2 "Functionalization of Cellulose" pp,
17-31 (Wiley-VCH, Weinheim, 1998); each of which is incorporated
herein by reference.
[0012] Another strategy involves functionalising the cellulose
backbone with a reactive double bond and polymerising in the
presence of monomers under conventional free radical polymerisation
conditions, see, e.g., U.S. Pat. No. 4,758,645. Alternatively, a
free radical initiator is covalently linked to the polysaccharide
backbone to generate a radical from the backbone to initiate
polymerisation and form graft copolymers (see, e.g., Bojanic V, J,
Appl. Polym. Sci., 60,1719-1725, 1996 and Zheng et al, ibid, 66,
307-317, 1997), For example, in U.S. Pat. No. 4,206,108, a thiol is
covalently bound to a polymeric backbone with pendent hydroxy
groups via a urethane linkage; this polymer containing mercapto
group is then reacted with ethylenically unsaturated monomers to
form the graft copolymer.
[0013] Unfortunately, none of these techniques lead to a
well-defined material with a controlled macrostructure, and
microstructure. For instance, none of these techniques leads to a
good control of both the number of graft chains per cellulose
backbone molecule and molecular weight of the graft chains.
Moreover, side reactions are difficult, if not impossible, to
avoid, including the formation of un-grafted polymer, graft chain
degradation and/or crosslinking of the grafted chains.
[0014] In an attempt to solve these problems, pre-formed chains
have been chemically grafted onto cellulosic polymers. For
instance, in U.S. Pat. No. 4,891,404, polystyrene chains were grown
in an anionic polymerization and capped with, e.g., CO.sub.2. These
grafts were then attached to mesylated or tosylated cellulose
triacetate by nucleophilic displacement. This method is difficult
to commercialise because of the stringent conditions required by
the method. Moreover, the set of monomers that can be used in this
method is restricted to non-polar olefins, thus precluding any
application in water media.
[0015] Block copolymers based on cellulose esters have been
reported. See, e.g., Oliveira et al, Polymer, 35, 9, 1994; Feger et
al, Polymer Bulletin, 3,407, 1980; Feger et al, Ibid, 6, 321, 1982;
U.S. Pat. No. 3,386,932; Steinmann, Polym. Preprint, Am. Chem. Soc.
Div. Polym. Chem. 1970, 11, 285; Kim et al, J. Polym. Sci. Polym,
Lett. Ed., 1973,11, 731; and Kim et al. J. Macromol. Sci., Chem (A)
1976,10, 671, each of which is incorporated herein by reference. A
major problem with these references is the generation of
considerable chain branching, grafting or crosslinking. Mezger et
al, Angew. Makromol Chem., 116,13,1983 prepared oligomeric,
monohydroxy-terminated cellulose coupled with
4,-4'-diphenyldisocyanate, which was then used as a
UV-macro-photo-initiator to prepare triblock copolymers. This
reaction is known as the iniferter technique and uses UV
initiation, which limits its applicability to certain processing
methods. Furthermore, it is typically applicable to styrenic and
methacrylic monomers. Other monomers, such as acrylics, vinyl
acetate, acrylamide type monomers, which are in widespread use in
waterborne systems, might require another technique.
[0016] So-called "living" radical polymerisation techniques are
known which can give better defined polymers in terms of molecular
structure. Three approaches to preparation of controlled polymers
in a "living" radical process have been described (Greszta et al,
Macromolecules, 27, 638 (1994)). The first approach involves the
situation where growing radicals react reversibly with scavenging
radicals to form covalent species. The second approach involves the
situation where growing radicals react reversibly with covalent
species to produce persistent radicals. The third approach involves
the situation where growing radicals participate in a degenerative
transfer reaction which regenerates the same type of radicals.
However, none of these techniques have been successfully applied to
polysaccharide substrates.
[0017] As mentioned above, it has previously been recognised in the
art that cellulose based materials adhere to cotton fibres. For
example, WO 00/18861 and WO 00/18862 disclose cellulosic compounds
having a benefit agent attached, so that the benefit agent will be
attached to the fibre. See also WO 99/14925. However, the ability
of polysaccharide, especially cellulose, based materials to adhere
has not been fully investigated, and a need exists to find
polysaccharide based materials that are of commercial
significance.
DEFINITION OF THE INVENTION
[0018] According to a first aspect of the invention, there is
provided a laundry cleaning composition comprising a graft polymer
benefit agent and at least one additional laundry cleaning
ingredient, the graft polymer benefit agent comprising a
polysaccharide backbone and a plurality of graft chains extending
from said backbone, each of said plurality of graft chains having a
degree of polymerisation between 5 and 250, preferably between 5
and 50 or between 25 and 250, wherein said graft polymer is
substantially free of cross-linking and has a degree of
substitution of grafts across a bulk sample in the range of from
0.02 to 1.0, preferably from 0.02 to 0.2 or from 0.1 to 1.0.
[0019] In the context of this specification, the term "cleaning"
means "washing and/or rinsing".
[0020] A second aspect of the invention provides a method of
delivering one or more laundry benefits in the cleaning of a
textile fabric, the method comprising contacting the fabric with a
graft polymer as defined above, preferably in the form of a laundry
cleaning composition a method of delivering one or more laundry
benefits in the washing of a textile fabric, the method comprising
contacting the fabric with a polymer as defined above, preferably
in the form of a laundry cleaning composition comprising said
polymer, and most preferably in the form of an aqueous dispersion
or solution of said composition. The method may also include the
further step of cleaning the fabric subsequently after wear or
use.
[0021] The second aspect of the invention may also be expressed as
use of a compound for delivering a benefit to a laundry item, the
compound being a graft polymer comprising a polysaccharide backbone
and a plurality of graft chains extending from said backbone, each
of said plurality of graft chains having a degree of polymerisation
between 5 and 250, preferably between 5 and 50 or between 25 and
250, wherein said graft polymer is substantially free of
cross-linking and has a degree of substitution of grafts across a
bulk sample in the range of from 6.02 to 1.0, preferably from 0.02
to 0.2 or from 0.1 to 1.0.
[0022] The second aspect of the invention may further be expressed
as use of a compound in the manufacture of a laundry cleaning
composition, the compound being a graft polymer comprising a
polysaccharide backbone and a plurality of graft chains extending
from said backbone, each of said plurality of graft chains having a
degree of polymerisation between 5 and 250, wherein said graft
polymer is substantially free of cross-linking and has a degree of
substitution of grafts across a bulk sample in the range of from
0.02 to 1.0.
[0023] When the benefit is soil release, the second aspect of the
invention may be expressed as a method of promoting soil release in
the washing of a textile fabric, the method comprising contacting
the fabric with a soil release polymer as defined above and
subsequently, after wear or use, washing the fabric.
[0024] This aspect may also be expressed as use of a compound for
promoting soil release during the washing of a textile fabric, the
compound being a graft polymer as defined above.
[0025] In addition, this aspect may be expressed as use of a soil
release polymer in the manufacture of a laundry cleaning
composition, the soil release polymer being a graft polymer as
defined above.
[0026] A third aspect of the invention provides a graft polymer as
defined above for deposition onto a fabric during a laundry
cleaning process.
[0027] The third aspect of the invention may also be expressed as a
method of depositing a benefit agent onto a fabric, the method
comprising applying a graft polymer or a composition as defined
above to the fabric.
[0028] The polysaccharide grafted and copolymeric materials
utilised in this invention with well defined macromolecular
features find utility in a wide field of applications. In
particular, due to their segmented structures, these polymers have
applicability as compatibilisers between naturally occurring
bio-polymers such as starch or cellulose with synthetic
thermoplastic resins, so-called biodegradable bio-plastics.
[0029] Furthermore, the polymers utilised in this invention may be
water soluble, or at least water-dispersible (e.g., water
swellable). In some of these embodiments, the cellulosic moiety is
known to adsorb to cellulosic surfaces, such as cotton or papers
which then alter the surface or interface of cotton/paper and bring
new benefits to the fibre or surface.
BRIEF DESCRIPTION OF THE DRAWINGS
[0030] FIG. 1 is a schematic drawing of the processes of this
invention for preparation of grafted polysaccharide materials and
copolymeric materials for use in the present invention.
[0031] FIG. 2 is a block diagram showing the various routes for
employing hydrolysis or saponification in the preparation of
cellulosic grafted or copolymeric materials.
[0032] FIG. 3 is a graft of a calibration plot in connection with
Example 2.
[0033] FIG. 4 is a graft showing the relationship between graft
length in cellulosic graft polymer to adsorbancy onto cotton
fibers.
[0034] FIGS. 5A and 5B are each graphs showing selected
experimental results from Example 3, with FIG. 5A showing the
amount of cellulosic graft THMMA polymer with a degree of
substitution of 0.023 deposited onto cotton fibres after a
treatment process and FIG. 5B showing results of a similar
experiment showing the amount of cellulosic graft THMMA polymer
with a degree of substitution of 0.18 deposited onto cotton fibres
after a treatment process.
[0035] FIG. 6 is a plot of grafts per chain versus graft degree of
polymerisation from Example 3.
DETAILED DESCRIPTION OF THE INVENTION
[0036] Benefits
[0037] The compounds which form the basis of the present invention
provide one or more of the following benefits, according to the
compound in question: soil release, anti-redeposition, soil
repellancy, colour care especially anti-dye transfer and dye
fixation, anti-wrinkling, ease of ironing, fabric rebuild,
anti-fibre damage, anti-pilling, anti-colour fading, dimensional
stability, good drape and body, waterproofing, fabric softening
and/or conditioning, fungicidal properties and insect
repellancy.
[0038] Definitions
[0039] The following definitions pertain to chemical structures,
molecular segments and substituents:
[0040] As used herein, the term "compound" includes materials of
any molecular weight, be they simple structures which are generally
considered to be monomers, dimers, trimers, higher oligomers as
well as polymers.
[0041] The phrase "having the structure" is not intended to be
limiting and is used in the same. way that the term "comprising" is
commonly used. The term "independently selected from the group
consisting of" is used herein to indicate that the recited
elements, e.g., R groups or the like, can be identical or
different.
[0042] "Optional" or "optionally" means that the subsequently
described event or occurrence may or may not occur, and that the
description includes instances where said event or circumstance
occurs and instances where it does not. For example, the phrase
"optionally substituted hydrocarbyl" means that a hydrocarbyl
moiety may or may not be substituted and that the description
includes both unsubstituted hydrocarbyl and hydrocarbyl where there
is substitution.
[0043] The term "alkyl" as used herein refers to a branched or
unbranched saturated hydrocarbon group typically although not
necessarily containing 1 to about 24 carbon atoms, such as methyl,
ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl,
decyl, and the like, as well as cycloalkyl groups such as
cyclopentyl, cyclohexyl and the like. Generally, although again not
necessarily, alkyl groups herein contain 1 to about 12 carbon
atoms. More preferably, an alkyl group, sometimes termed a "lower
alkyl" group, contains one to six carbon atoms, preferably one to
four carbon atoms. "Substituted alkyl" refers to alkyl substituted
with one or more substituent groups, and the terms
"heteroatom-containing alkyl" and "heteroalkyl" refer to alkyl in
which at least one carbon atom is replaced with a heteroatom.
[0044] The term "alkenyl" as used herein refers to a branched or
unbranched hydrocarbon group typically although not necessarily
containing 2 to about 24 carbon atoms and at least one double bond,
such as ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl,
octenyl, decenyl, and the like. Generally, although again not
necessarily, alkenyl groups herein contain 2 to about 12 carbon
atoms. More preferably, an alkenyl group, sometimes termed a "lower
alkenyl" group, contains two to six carbon atoms, preferably two to
four carbon atoms. "Substituted alkenyl" refers to alkenyl
substituted with one or more substituent groups, and the terms
"heteroatom-containing alkenyl" and "heteroalkenyl" refer to
alkenyl in which at least one carbon atom is replaced with a
heteroatom.
[0045] The term "alkynyl" as used herein refers to a branched or
unbranched hydrocarbon group typically although not necessarily
containing 2 to about 24 carbon atoms and at least one triple bond,
such as ethynyl, n-propynyl, isopropynyl, n-butynyl, isobutynyl,
octynyl, decynyl, and the like. Generally, although again not
necessarily, alkynyl groups herein contain 2 to about 12 carbon
atoms. More preferably, an alkynyl group, sometimes termed a "lower
alkynyl" group, contains two to six carbon atoms, preferably three
or four carbon atoms. "Substituted alkynyl" refers to alkynyl
substituted with one or more substituent groups, and the terms
"heteroatom-containing alkynyl" and "heteroalkynyl" refer to
alkynyl in which at least one carbon atom is replaced with a
heteroatom.
[0046] The term "alkoxy" as used herein intends an alkyl group
bound through a single, terminal ether linkage; that is, an
"alkoxy" group may be represented as --O-alkyl where alkyl is as
defined above. More preferably, an alkoxy group, sometimes termed a
"lower alkoxy" group, contains one to six, more preferably one to
four, carbon atoms. The term "aryloxy" is used in a similar
fashion, with aryl as defined below.
[0047] Similarly, the term "alkyl thio" as used herein intends an
alkyl group bound through a single, terminal thioether linkage;
that is, an "alkyl thio" group may be represented as --S-alkyl
where alkyl is as defined above. More preferably, an alkylthio
group, sometimes termed a "lower alkyl thio" group, contains one to
six, more preferably one to four, carbon atoms.
[0048] The term "allenyl" is used herein in the conventional sense
to refer to a molecular segment having the structure
--CH.dbd.C.dbd.CH.sub.2- . An "allenyl" group may be unsubstituted
or substituted with one or more non-hydrogen substituents.
[0049] The term "aryl" as used herein, and unless otherwise
specified refers to an aromatic substituent containing a single
aromatic ring or multiple aromatic rings that are fused together,
linked covalently, or linked to a common group such as a methylene
or ethylene moiety. The common linking group may also be a carbonyl
as in benzophenone, an oxygen atom as in diphenylether, or a
nitrogen atom as in diphenylamine, Preferred aryl groups contain
one aromatic ring or two fused or linked aromatic rings, e.g.,
phenyl, naphthyl, biphenyl, diphenylether, diphenylamine,
benzophenone, and the like. In particular embodiments, aryl
substituents have 1 to about 200 carbon atoms, typically 1 to about
50 carbon atoms, and preferably 1 to about 20 carbon atoms. More
preferably, aryl groups contain from 6 to 18, preferably 6 to 16
and especially 6 to 14, carbon atoms. Phenyl and naphthyl,
particularly phenyl, groups are especially preferred. "Substituted
aryl" refers to an aryl moiety substituted with one or more
substituent groups, (e.g., tolyl, mesityl and perfluorophenyl) and
the terms "heteroatom-containing aryl" and "heteroaryl" refer to
aryl in which at least one carbon atom is replaced with a
heteroatom.
[0050] The term "aralkyl" refers to an alkyl group with an aryl
substituent, and the term "aralkylene" refers to an alkylene group
with an aryl substituent; the term "alkaryl" refers to an aryl
group that has an alkyl substituent, and the term "alkarylene"
refers to an arylene group with an alkyl substituent. Preferred
aralkyl groups contain from 7 to 16, especially 7 to 10, carbon
atoms, a particularly preferred aralkyl group being a benzyl
group.
[0051] The terms "halo" and "halogen" are used in the conventional
sense to refer to a chloro, bromo, fluoro or iodo substituent. The
terms "haloalkyl," "haloalkenyl" or "haloalkynyl" (or "halogenated
alkyl", "halogenated alkenyl," or "halogenated alkynyl") refer to
an alkyl, alkenyl or alkynyl group, respectively; in which at least
one of the hydrogen atoms in the group has been replaced with a
halogen atom.
[0052] The term "heteroatom-containing" as in a
"heteroatom-containing hydrocarbyl group" refers to a molecule or
molecular fragment in which one or more carbon atoms is replaced
with an atom other than carbon, e.g., nitrogen, oxygen, sulfur,
phosphorus or silicon. Similarly, the term "heteroalkyl" refers to
an alkyl substituent that is heteroatom-containing, the term
"heterocyclic" refers to a cyclic substituent that is
heteroatom-containing, the term "heteroaryl" refers to an aryl
substituent that is heteroatom-containing, and the like. When the
term "heteroatom-containing" appears prior to a list of possible
heteroatom-containing groups, it is intended that the term apply to
every member of that group. That is, the phrase
"heteroatom-containing alkyl, alkenyl and alkynyl" is to be
interpreted as "heteroatom-containing alkyl, heteroatom-containing
alkenyl and heteroatom-containing alkynyl." Preferably, a
heterocyclic group is 3- to 18-membered, particularly a 3- to
14-membered, and especially a 5- to 10-membered ring system
containing at least one heteroatom.
[0053] "Hydrocarbyl" refers to univalent hydrocarbyl radicals
containing 1 to about 30 carbon atoms, preferably 1 to about 24
carbon atoms, most preferably 1 to about 12 carbon atoms, including
branched or unbranched, saturated or unsaturated species, such as
alkyl groups, alkenyl groups, aryl groups, and the like. The term
"lower hydrocarbyl" intends a hydrocarbyl group of one to six
carbon atoms, preferably one to four carbon atoms. "Substituted
hydrocarbyl" refers to hydrocarbyl substituted with one or more
substituent groups, and the term "heteroatom-containing
hydrocarbyl" and "heterohydrocarbyl" refer to hydrocarbyl in which
at least one carbon atom is replaced with a heteroatom.
[0054] By "substituted" as in "substituted hydrocarbyl,"
"substituted aryl," "substituted alkyl," "substituted alkenyl" and
the like, as alluded to in some of the aforementioned definitions,
is meant that in the hydrocarbyl, hydrocarbylene, alkyl, alkenyl or
other moiety, at least one hydrogen atom bound to a carbon atom is
replaced with one or more substituents that are functional groups
such as hydroxyl, alkoxy, thio, phosphino, amino, halo, silyl, and
the like. When the term "substituted" appears prior to a list of
possible substituted groups, it is intended that the term apply to
every member of that group. That is, the phrase "substituted alkyl,
alkenyl and alkynyl" is to be interpreted as "substituted alkyl, *
substituted alkenyl and substituted alkynyl". Similarly,
"optionally substituted alkyl, alkenyl and alkynyl" is to be
interpreted as "optionally substituted alkyl, optionally
substituted alkenyl and optionally substituted alkynyl."
[0055] When any of the foregoing substituents are designated as
being optionally substituted, the substituent groups which are
optionally present may be any one or more of those customarily
employed in the development of laundry treatment compounds and/or
the modification of such compounds to influence their
structure/activity, stability, or other property. Specific examples
of such substituents include, for example, halogen atoms, nitro,
cyano, hydroxyl, cycloalkyl, alkyl, haloalkyl, cycloalkyloxy,
alkoxy, haloalkoxy, amino, alkylamino, dialkylamino, formyl,
alkoxycarbonyl, carboxyl, alkanoyl, alkylthio, alkylsulphinyl,
alkylsulphonyl, alkylsulphonato, carbamoyl and alkylamido groups.
When any of the foregoing substituents represents or contains an
alkyl substituent group, this may be linear or branched and may
contain up to 12, preferably up to 6, and especially up to 4,
carbon atoms. A cycloalkyl group may contain from 3 to 8,
preferably from 3 to 6, carbon atoms. A halogen atom may be a
fluorine, chlorine, bromine or iodine atom and any group which
contains a halo moiety, such as a haloalkyl group, may thus contain
any one or more of these halogen atoms.
[0056] As used herein the term "silyl" refers to the
--SiZ.sup.1Z.sup.2Z.sup.3 radical, where each of Z.sup.1, Z.sup.2,
and Z.sup.3 is independently selected from the group consisting of
hydrido and optionally substituted alkyl, alkenyl, alkynyl, aryl,
aralkyl, alkaryl, heterocyclic, alkoxy, aryloxy and amino.
[0057] As used herein, the term "phosphino" refers to the group
--PZ.sup.1Z.sup.2, where each of Z.sup.1 and Z.sup.2 is
independently selected from the group consisting of hydrido and
optionally substituted alkyl, alkenyl, alkynyl, aryl, aralkyl,
alkaryl, heterocyclic and amino.
[0058] The term "amino" is used herein to refer to the group
--NZ.sup.1Z.sup.2, where each of Z.sup.1 and Z.sup.2 is
independently selected from the group consisting of hydrido and
optionally substituted alkyl, alkenyl, alkynyl, aryl, aralkyl,
alkaryl and heterocyclic.
[0059] The term "thio" is used herein to refer to the group
--SZ.sup.1, where Z.sup.1 is selected from the group consisting of
hydrido and optionally substituted alkyl, alkenyl, alkynyl, aryl,
aralkyl, alkaryl and heterocyclic.
[0060] As used herein all reference to the elements and groups of
the Periodic Table of the Elements is to the version of the table
published by the Handbook of Chemistry and Physics, CRC Press,
1995, which sets forth the new IUPAC system for numbering
groups.
[0061] The term "soil release polymer" is used in the art to cover
polymeric materials which assist release of soil from fabrics, e.g.
cotton or polyester based fabrics. For example, it is used in
relation to polymers which assist release of soil direct from
fibres. It is also used to refer to polymers which modify the
fibres so that dirt adheres to the polymer-modified fibres rather
than to the fibre material itself. Then, when the fabric is washed
the next time, the dirt is more easily removed than if it was
adhering the fibres. Although not wishing to be bound by any
particular theory or explanation, the inventors believe that those
compounds utilised in the present invention which deliver a soil
release benefit, probably exert their effect mainly by the latter
mechanism.
[0062] As those of skill in the art of polysaccharide, especially
cellulosic, polymers recognise, the term "degree of substitution"
(or DS) refers to substitution of the functional groups on the
repeating sugar unit. In the case of cellulosic polymers, DS refers
to substitution of the three hydroxyl groups on the repeating
anhydroglucose unit. Thus, for cellulose polymers, the maximum
degree of substitution is 3. DS values do not generally relate to
the uniformity of substitution of chemical groups along the
polysaccharide molecule and are not related to the molecular weight
of the polysaccharide backbone. The average degree of substitution
groups is preferably from 0.1 to 3 (e.g. from 0.3 to 3), more
preferably from 0.1 to 1 (e.g. from 0.3 to 1).
[0063] The Polysaccharide Before Substitution
[0064] As used herein, the term "polysaccharides" includes natural
polysaccharides, synthetic polysaccharides, polysaccharide
derivatives and modified polysaccharides. Suitable polysaccharides
for use in the treating compositions of the present invention
include, but are not limited to, gums, arabinans, galactans, seeds
and mixtures thereof as well as cellulose and derivatives
thereof.
[0065] Suitable polysaccharides that are useful in the present
invention include polysaccharides with a degree of polymerisation
(DP) over 40, preferably from about 50 to about 100,000, more
preferably from about 500 to about 50,000. Constituent saccharides
preferably include, but are not limited to, one or more of the
following saccharides: isomaltose, isomaltotriose,
isomaltotetraose, isomaltooligosaccharide, fructooligosaccharide,
levooligosaccharides, galactooligosaccharide, xylooligosaccharide,
gentiooligosaccharides, disaccharides, glucose, fructose,
galactose, xylose, mannose, sorbose, arabinose, rhamnose, fucose,
maltose, sucrose, lactose, maltulose, ribose, lyxose, allose,
altrose, gulose, idose, talose, trehalose, nigerose, kojibiose,
lactulose, oligosaccharides, maltooligosaccharides, trisaccharides,
tetrasaccharides, pentasaccharides, hexasaccharides,
oligosaccharides from partial hydrolysates of natural
polysaccharide sources and mixtures thereof.
[0066] The polysaccharides can be extracted from plants, produced
by organisms, such as bacteria, fungi, prokaryotes, eukaryotes,
extracted from animal and/or humans. For example, xanthan gum can
be produced by Xanthomonas campestris, gellan by Sphingomonas
paucimobilis, xyloglucan can be extracted from tamarind seed.
[0067] The polysaccharides can be linear, or branched in a variety
of ways, such as 1-2, 1-3, 1-4, 1-6, 2-3 and mixtures thereof. Many
naturally occurring polysaccharides have at least some degree of
branching, or at any rate, at least some saccharide rings are in
the form of pendant side groups on a main polysaccharide
backbone.
[0068] It is desirable that the polysaccharides of the present
invention have a molecular weight in the range of from about 10,000
to about 10,000,000, more preferably from about 50,000 to about
1,000,000, most preferably from about 50,000 to about 500,000.
[0069] Preferably, the polysaccharide is selected from the group
consisting of: tamarind gum (preferably consisting of xyloglucan
polymers), guar gum, locust bean gum (preferably consisting of
galactomannan polymers), and other industrial gums and polymers,
which include, but are not limited to, Tara, Fenugreek, Aloe, Chia,
Flaxseed, Psyllium seed, quince seed, xanthan, gellan, welan,
rhamsan, dextran, curdlan, pullulan, scleroglucan, schizophyllan,
chitin, hydroxyalkyl cellulose, arabinan (preferably from sugar
beets), de-branched arabinan (preferably from sugar beets),
arabinoxylan (preferably from rye and wheat flour), galactan
(preferably from lupin and potatoes), pectic galactan (preferably
from potatoes), galactomannan (preferably from carob, and including
both low and high viscosities), glucomannan, lichenan (preferably
from icelandic moss), mannan (preferably from ivory nuts),
pachyman, rhamnogalacturonan, acacia gum, agar, alginates,
carrageenan, chitosan, clavan, hyaluronic acid, heparin, inulin,
cellodextrins, cellulose, cellulose derivatives and mixtures
thereof. These polysaccharides can also be treated (preferably
enzymatically) so that the best fractions of the polysaccharides
are isolated.
[0070] Polysaccharides can be used which have an .alpha.- or
.beta.-linked backbone. However, more preferred polysaccharides
have a .beta.-linked backbone, preferably a .beta.-1,4-linked
backbone. It is preferred that the .beta.-1,4-linked polysaccharide
is cellulose, a cellulose derivative, particularly cellulose
sulphate, cellulose acetate, sulphoethylcellulose,
cyanoethylcellulose, methyl cellulose, ethyl cellulose,
carboxymethylcellulose, hydroxyethylcellulose or
hydroxypropylcellulose; a xyloglucan, particularly one derived from
Tamarind seed gum, a glucomannan, particularly Konjac glucomannan;
a galactomannan, particularly Locust Bean gum or Guar gum; a side
chain branched galactomannan, particularly Xanthan gum; chitosan or
a chitosan salt. Other .beta.-1,4-linked polysaccharides having an
affinity for cellulose, such as mannan are also preferred.
[0071] Xyloglucan polymer is a highly preferred polysaccharide for
use in the laundry and/or fabric care compositions of the present
invention. Xyloglucan polymer is preferably obtained from tamarind
seed polysaccharides. The preferred range of molecular weights for
the xyloglucan polymer is from about 10,000 to about 1,000,000 more
preferably from about 50,000 to about 200,000.
[0072] Polysaccharides, are normally incorporated in the treating
composition of the present invention at levels from about 0.01% to
about 25%, preferably from about 0.5% to 20%, more preferably from
1 to 15% by weight of the treating composition.
[0073] Polysaccharides have a high affinity for binding with
cellulose. Without wishing to be bound by theory, it is believed
that the binding efficacy of the polysaccharides to cellulose
depends on the type of linkage, extent of branching and molecular
weight. The extent of binding also depends on the nature of the
cellulose (i.e., the ratio of crystalline to amorphous regions in
cotton, rayon, linen, etc.).
[0074] The natural polysaccharides can be modified with amines
(primary , secondary, tertiary), amides, esters, ethers, urethanes,
alcohols, carboxylic acids, tosylates, sulfonates, sulfates,
nitrates, phosphates and mixtures thereof. Such a modification can
take place in position 2, 3 and/or 6 of the saccharide unit. Such
modified or derivatised polysaccharides can be included in the
compositions of the present invention in addition to the natural
polysaccharides.
[0075] Nonlimiting examples of such modified polysaccharides
include: carboxyl and hydroxymethyl substitutions (e.g. glucuronic
acid instead of glucose); amino polysaccharides (amine
substitution, e.g. glucosamine instead of glucose); C.sub.1-C.sub.6
alkylated polysaccharides; acetylated polysaccharide ethers;
polysaccharides having amino acid residues attached (small
fragments of glycoprotein); polysaccharides containing silicone
moieties. Suitable examples of such modified polysaccharides are
commercially available from Carbomer and include, but are not
limited to, amino alginates, such as hexanediamine alginate, amine
functionalised cellulose-like O-methyl-(N-1,12-dodecanediamine)
cellulose, biotin heparin, carboxymethylated dextran, guar
polycarboxylic acid, carboxymethylated locust bean gum,
carboxymethylated xanthan, chitosan phosphate, chitosan phosphate
sulfate, diethylaminoethyl dextran, dodecylamide alginate, sialic
acid, glucuronic acid, galacturonic acid, mannuronic acid,
guluronic acid, N-acetylgluosamine, N-acetylgalactosamine, and
mixtures thereof.
[0076] Especially preferred polysaccharides include cellulose,
ether, ester and urethane derivatives of cellulose, particularly
cellulose monoacetate, xyloglucans and galactomannans, particularly
Locust Bean gum.
[0077] It is preferred that the polysaccharide has a total number
of sugar units from 10 to 7000, although this figure will be
dependent on the type of polysaccharide chosen, at least to some
extent.
[0078] In the case of cellulose and water-soluble modified
celluloses, the total number of sugar units is preferably from 50
to 1 000, more preferably 50 to 750 and especially 200 to 300. The
preferred molecular weight of such polysaccharides is from 10 000
to 150000.
[0079] In the case of cellulose monoacetate, the total number of
sugar units is from 10 to 200, preferably 100 to 150. The preferred
molecular weight is from 10 000 to 20 000.
[0080] In the case of Locust Bean gum, the total number of sugar
units is preferably from 50 to 7000. The preferred molecular weight
is from 10 000 to 1000 000.
[0081] In the case of xyloglucan, the total number of sugar units
is preferably from 1000 to 3000. the preferred molecular weight is
from 250 000 to 600 000.
[0082] The polysaccharide can be linear, like in hydroxyalkyl
cellulose, it can have an alternating repeat like in carrageenan,
it can have an interrupted repeat like in pectin, it can be a block
copolymer like in alginate, it can be branched like in dextran, or
it can have a complex repeat like in xanthan. Descriptions of the
polysaccharides are given in "An introduction to Polysaccharide
Biotechnology", by M. Tombs and S. E. Harding, T. J. Press
1998.
[0083] Preferred polysaccharides are celluloses or cellulose
derivatives of formula (A): 1
[0084] wherein at least one or more R groups are independently
selected from groups of formulae: 2
[0085] wherein each R.sup.1 is independently selected from
C.sub.1-20 (preferably C.sub.1-6) alkyl, C.sub.2-20 (preferably
C.sub.2-6) alkenyl (e.g. vinyl) and C.sub.5-7 aryl (e.g. phenyl)
any of which is optionally substituted by one or more substituents
independently selected from C.sub.1-4 alkyl, C.sub.1-12 (preferably
C.sub.1-4) alkoxy, hydroxyl, vinyl and phenyl groups;
[0086] each R.sup.2 is independently selected from hydrogen and
groups R.sup.1 as hereinbefore defined;
[0087] R.sup.3 is a bond or is selected from C.sub.1-4 alkylene,
C.sub.2-4 alkenylene and C.sub.5-7 arylene (e.g. phenylene) groups,
the carbon atoms in any of these being optionally substituted by
one or more substituents independently selected from C.sub.1-12
(preferably C.sub.1-4) alkoxy, vinyl, hydroxyl, halo and amine
groups;
[0088] each R.sup.4 is independently selected from hydrogen,
counter cations such as alkali metal (preferably Na) or 1/2 Ca or
1/2 Mg, and groups R.sup.1 as hereinbefore defined;
[0089] R.sup.5 is selected from C.sub.1-20 (preferably C.sub.1-6)
alkyl, C.sub.2-20 (preferably C.sub.2-6) alkenyl (e.g. vinyl) and
C.sub.5-7 aryl (e.g. phenyl) any of which is optionally substituted
by one or more substituents independently selected from C.sub.1-4
alkyl, C.sub.1-12 (preferably C.sub.1-4) alkoxy, hydroxyl,
carboxyl, cyano, sulfonato, vinyl and phenyl groups; and
[0090] groups R which together with the oxygen atom forming the
linkage to the respective saccharide ring forms an ester or
hemi-ester group of a tricarboxylic- or higher polycarboxylic- or
other complex acid such as citric acid, an amino acid, a synthetic
amino acid analogue or a protein;
[0091] any remaining R groups being selected from hydrogen and
ether substituents.
[0092] For the avoidance of doubt, as already mentioned, in formula
(A), some of the R groups may optionally have one or more
structures, for example as hereinbefore described. For example, one
or more R groups may simply be hydrogen or an alkyl group.
[0093] Preferred groups may for example be independently selected
from one or more of acetate, propanoate, trifluoroacetate,
2-(2-hydroxy-1-oxopropo- xy) propanoate, lactate, glycolate,
pyruvate, crotonate, isovalerate cinnamate, formatter, salicylate,
carbamate, methylcarbamate, benzoate, gluconate, methanesulphonate,
toluene, sulphonate, groups and hemiester groups of fumaric,
malonic, itaconic, oxalic, maleic, succinic, tartaric, aspartic,
glutamic, and malic acids.
[0094] Particularly preferred such groups are the monoacetate,
hemisuccinate, and 2-(2-hydroxy-1-oxopropoxy)propanoate. The term
"monoacetate" is used herein to denote those acetates with a degree
of substitution of about 1 or less on a cellulose or other
.beta.-1,4 polysaccharide backbone. Thus, "cellulose monoacetate"
refers to a molecule that has acetate esters in a degree of
substitution of about 1.1 or less, preferably about 1.1 to about
0.5. "Cellulose triacetate" refers to a molecule that has acetate
esters in a degree of substitution of about 2.7 to 3.
[0095] Cellulose esters of hydroxyacids can be obtained using the
acid anhydride in acetic acid solution at 20-30.degree. C. and in
any case below 50.degree. C. When the product has dissolved the
liquid is poured into water (b.p. 316,160). Tri-esters can be
converted to secondary products as with the triacetate. Glycollic
and lactic ester are most common.
[0096] Cellulose glycollate may also be obtained from cellulose
chloracetate (GB-A-320 842) by treating 100 parts with 32 parts of
NaOH in alcohol added in small portions.
[0097] An alternative method of preparing cellulose esters consists
in the partial displacement of the acid radical in a cellulose
ester by treatment with another acid of higher ionisation constant
(FR-A-702 116). The ester is heated at about 100.degree. C. with
the acid which, preferably, should be a solvent for the ester. By
this means cellulose acetate-oxalate, tartrate, maleate, pyruvate,
salicylate and phenylglycollate have been obtained, and from
cellulose tribenzoate a cellulose benzoate-pyruvate. A cellulose
acetate-lactate or acetate-glycollate could be made in this way
also. As an example cellulose acetate (10 g.) in dioxan (75 ml.)
containing oxalic acid (10 g.) is heated at 100.degree. C. for 2
hours under reflux.
[0098] Multiple esters are prepared by variations of this process.
A simple ester of cellulose, e.g. the acetate, is dissolved in a
mixture of two (or three) organic acids, each of which has an
ionisation constant greater than that of acetic acid
(1.82.times.10.sup.-5). With solid acids suitable solvents such as
propionic acid, dioxan and ethylene dichloride are used. If a mixed
cellulose ester is treated with an acid this should have an
ionisation constant greater than that of either of the acids
already in combination.
[0099] A cellulose acetate-lactate-pyruvate is prepared from
cellulose acetate, 40 per cent. acetyl (100 g.), in a bath of 125
ml. pyruvic acid and 125 ml. of 85 per cent. lactic acid by heating
at 100.degree. C. for 18 hours. The product is soluble in water and
is precipitated and washed with ether-acetone. M.p. 230-250.degree.
C.
[0100] In the case when solubilising groups are attached to the
polysaccharide, this is typically via covalent bonding and, may be
pendant upon the backbone or incorporated therein. The type of
solubilising group may alter according to where the group is
positioned with respect to the backbone.
[0101] The molecular weight of the substituted polysaccharide part
may typically be in the range of 1,000 to 2,000,000, for example
10,000 to 1,500,000.
[0102] The Polymer and its Synthesis
[0103] The invention utilises a compound which in most preferred
embodiments is a cellulosic graft polymer, which is prepared from
control agents for the living or controlled free radical
polymerisation of the graft segments. In another aspect, the
invention is a cellulosic copolymer, which is prepared from control
agents for the living or controlled free radical polymerisation of
monomers into blocks, The production of these two categories of
polymers is generally shown in FIG. 1. As shown therein, a
cellulosic starting material (e.g., cellulosic backbone) is
optionally first depolymerised to a desired size. Then following
route a in FIG. 1, initiator control agents (designated herein as
Y) are attached to at least some middle portions of the cellulosic
material. Following route b in FIG. 1, initiator-control agents are
attached to at least one terminal end portion of the cellulosic
backbone. Desired one or more monomers are then polymerised in a
controlled or living-type free radical method to yield cellulosic
backbone graft polymers from route a and block copolymers from
route b, with the rectangular blocks representing the graft or
block polymer segments.
[0104] FIG. 2 shows the processes for synthesis of the polymers of
this invention in block diagram form. As shown in FIG. 2, the
cellulosic starting material is optionally, but typically,
depolymerised to obtain a cellulosic material having a desired
size. Thereafter, the process proceeds in one of two routes. In a
first route, after depolymerisation the cellulosic material is
optionally subjected to hydrolysis or saponification, depending on
the starting material. The purpose of hydrolysis or saponification
is to make the cellulosic material more water soluble (or at least
water dispersible by reducing the degree of substitution, as
explained more fully below). Following the same first route, the
cellulosic material is substituted with one or more
initiator-control agents. The substituted material is then
subjected to polymerisation conditions with one or more monomers of
choice in order to polymerise the one or more monomers at the
points of attachment of the initiator control agents. This
polymerisation step is preferably performed under living or
controlled type kinetics (although some loss of control is
conceivable). The alternative second route shown in FIG. 2 is where
the hydrolysis or saponification step is performed after the
polymerisation step and is an alternative depending on the starting
cellulosic material.
[0105] Thus, cellulosic based polymers, and other polysaccharide
based polymers, can be prepared according to the general schemes
indicated in FIG. 2. Basically, they can be graft copolymers
composed of a cellulosic backbone and synthetic polymeric chains
grafted to it or block copolymers wherein the cellulosic segment is
linked to another synthetic polymeric chain at either one or both
ends.
[0106] As shown in FIG. 2, grafted copolymers are typically
prepared by:
[0107] 1. depolymerising the polysaccharide, preferably cellulosic,
backbone material to the desired molecular weight;
[0108] 2. attaching the control agent along the polysaccharide,
preferably cellulosic, backbone;
[0109] 3. polymerising at least one monomer in a living or
controlled free radical polymerisation, with the purpose of growing
the grafted chain to a targeted molecular weight; and
[0110] 4. optionally, saponifying/hydrolysing the polysaccharide,
preferably cellulosic, backbone.
[0111] Block copolymers are prepared according the same scheme with
the exception that the control agents are selectively anchored to
the termini of the polysaccharide, preferably cellulosic,
chains.
[0112] Depolymerization
[0113] Polymers utilised in this invention generally have a
cellulosic backbone selected from the group consisting of
cellulose, modified cellulose and hemi-cellulose. Modified
cellulose and hemi-cellulose are used herein consistently with as
those of skill in the art would use such terms, including for
example, cellulosic materials having at least some
.beta.-1,4-linked glucose units in the backbone, such as mannan,
glucomannan and xyloglucan. The cellulosic backbone may be
naturally occurring and may be straight chained or branched. In
preferred embodiments, the cellulosic backbone is cellulose
triacetate or cellulose monoacetate. The cellulosic backbone may be
obtained from commercial sources, but in preferred embodiments, a
cellulosic backbone obtained from such sources is de-polymerized
prior to preparation of the grafts or copolymers.
[0114] Cellulosic materials are preferably those obtained from the
esterification of natural or regenerated cellulose. Cellulose
esters such as cellulose mono-, di- and tri-acetate, or as
cellulose mono-, di- and tri-propionate are preferred.
Depolymerisation is performed according to known procedures. For
instance, one can start from microcrystalline cellulose, that is
successively hydrolysed in fuming HCl in cellulose oligomers, then
isolated and re-acetylated in triacetate cellulose (Flugge L. A et
al., J. Am. Chem. Soc. 1999, 121, 7228-7238). This process works
well when very low molecular weights are targeted, for example for
a degree of polymerisation of about 8 and below. Other processes
start from cellulose esters with a DS between 2.7 and 3 (e.g.,
fully esterified cellulose), which are contacted either with
Bronsted acid, such as HBr (De Oliveira W. et al, Cellulose, 1994,
1, 77-86), or Lewis acid such as BF.sub.3 (U.S. Pat. No.
3,386,932). Each of these references is incorporated herein by
reference, Molecular weight control of the cellulosic backbone is
achieved by adjusting the reaction conditions, like temperature,
time of contact and concentration of the acid, etc.
[0115] Whether depolymerisation is carried out or not, the
cellulosic backbone has a number average molecular weight in the
range of from about 3,000 to about 100,000, more preferably in the
range of from about 3,000 to about 60,000 and most preferably in
the range of from about 3,000 to about 20,000. Depending on the
exact type of cellulose, the degree of polymerisation can range
from about 15 to about 250, more preferably from about 15 to about
100, and most preferably from about 15 to about 80.
[0116] Depending on the starting material (e.g., cellulose
triacetate or cellulose monoacetate), the cellulosic backbone
polymer optionally may be hydrolysed or saponified. Hydrolysis or
saponification may optionally be performed on the graft or block
copolymers of this invention after the grafts or blocks have been
grown from the cellulosic backbone. The purpose of this step in the
process is to provide water solubility or dispersability to the
cellulosic graft or block copolymers utilised in this invention.
The term "water soluble or dispersible" as used herein means that
the graft or block copolymers are either freely soluble in or
dispersible (as a stable suspension) in at least water or a
buffered water solution. "Soluble" and/or "miscible" herein means
that the copolymer dissolves in the solvent or solvents at
25.degree. C. at a concentration of at least about 0.1 mg/mL, more
preferably about 1 mg/mL, and most preferably about 2 mg/mL.
"Dispersible" means that the copolymer forms a stable suspension
(without the addition of further materials such as emulsifiers)
when combined with the solvent or solvents at about 25.degree. C.
at a concentration of at least about 0.1 mg/mL, more preferably
about 1 mg/mL, and most preferably about 2 mg/mL. Hydrolysis or
saponification are carried out substantially according to methods
known to those of skill in the art. Hydrolysis is carried out by
reacting the cellulosic backbone with an acid, such as acetic acid.
Generally, the deacetylation/hydrolysis is carried out in a mix of
acetic acid, water and methanol at an appropriate temperature
(e.g., about 155.degree. C.) in an appropriate vessel (e.g. a
sealed reactor). Typical reaction times are 9 to 12 hrs. The
product is isolated by precipitation into acetone and yields a
water soluble/dispersible form of cellulosic material (acetate
DS-0.75-1.25), See, for example, WO 00/22224, which is incorporated
herein by reference. Saponification, generally, is carried out by
reacting the cellulosic backbone material with a base, such as NaOH
or KOH. Typically, a solution of the cellulosic backbone material
in a solvent (e.g., dimethylformamide (DMF) or tetrahydrofuran
(THF), for example in a concentration of 10 to 25 weight %) is
added into an aqueous solution of the base (for example, in a
concentration 0.1 M to 1 M preferably between 0.1 M to 0.5M, at
temperatures between 25.degree. C. and 80.degree. C., preferably
between 40.degree. C. and 60.degree. C. to make up a total polymer
concentration of 10000 ppm).
[0117] The cellulosic backbone is substituted (sometimes referred
to as "activated") with a desired degree of substitution of
initiator-control agent adducts so that grafts or blocks may be
polymerised or grown from the sites of attachment of the initiator
control agent adducts. Because polymerisation will appear to have
occurred between the bond of the initiator and control agent, the
initiator fragment or the control agent fragment may be attached to
the cellulosic backbone, such that the substituted material may be
characterized by the general formula I: 3
[0118] where SU represents a sugar unit in the cellulosic material,
L is an optional linker, Y is the initiator control agent adduct or
chain transfer agent (collectively generally referred to herein as
a "control agent"), a is the number of sugar units that do not have
a Y substitution and is typically in the range of from about 3-80,
b is the number of sugar units that have at least one Y
substitution and is typically in the range of from about 1-25, c is
0 or 1 depending on whether a linker is present, and d is the
degree of substitution of Y control agents on a single sugar unit
and is typically in the range of from about 1-3. The sugar units
may be placed in any order and there may be many more unsubstituted
sugar units (SU).sub.a than substituted sugar units (SU).sub.b.
Moreover, formula (I) shows the middle sugar units of the
cellulosic backbone, but the copolymer embodiment of this invention
has the Y substituents placed on at least one terminal end sugar
unit. Thus, formula (I) may appear as 4
[0119] In some preferred embodiments, a, b and d are numbers that
will give the graft or block copolymers of this invention the
desired level of adherence to the surface or fibre. In other words,
a, b and d control the properties of the resultant polymer. Since
it is an object of this invention to provide a grafted or copolymer
cellulosic material that adheres to cotton or other fibres or
surfaces, then control of a, b and c may be critical to the
invention.
[0120] As those of skill in the art will appreciate, a, b and d are
typically determined from a bulk sample by nuclear magnetic
resonance (NMR), gel permeation chromatography (GPC) or some other
spectroscopic or chromatographic technique. Thus, a and b are
average numbers across the bulk sample and they may not be
integers. Using formula (I), the number of grafts per chain is
calculated by multiplying b times d. The graft density for a bulk
sample is determined by the formula (b*d)/(a+b), where the average
graft density for a bulk sample is determined by NMR or another
spectroscopic technique and (a+b) is determined on average by GPC
or another chromatographic technique. These two measurements will
allow for calculation of the number of grafts per chain (b*d). In
preferred embodiments, graft density for a bulk sample is in the
range of from about 0.005 to about 3, more preferably in the range
of from about 0.01 to about 1 and even more preferably in the range
of from about 0.05 to about 0.15. The number of grafts per chain is
preferably in the range of from about 1 to about 75 and more
preferably in the range of from about 1 to 20.
[0121] In formula (I), Y is the initiator control agent adduct,
iniferter or chain transfer agent, which is the portion that
provides control of the free radical polymerisation process, and is
thus generally referred to herein as the control agent (CA). This
portion of the molecule can include an initiating portion or not,
depending on the method of polymerisation being employed. One
preferred embodiment is where Y is a control agent without an
initiating fragment (i.e. -CA). When an initiator fragment is
present, Y may be either -I-CA or -CA-I, where CA refers to a
control agent moiety and I refers to an initiator moiety or
fragment. Therefore the number of grafts can be defined by the
number of attachment points of a -I-CA or -CA group. When an
initiating fragment is present in Y, the -I-CA embodiment is
generally preferred. In addition to the NMR, GPC and other
spectroscopic techniques discussed above, the number of Y
attachment points may be determined by enzymatic digestion of the
cellulosic backbone to glucose. This method is known to those
skilled in the art and typically involves a GPC measurement for
number average molecular weight with a calculation to obtain the
number of chains.
[0122] Y may be selected from those control agents that provide
living-type kinetics to the polymerisation of at least one monomer
from the site of attachment of the control agent. Typically, the
control agent must be able to be expelled as or support a free
radical. In some embodiments, Y is characterized by the general
formula II: 5
[0123] where Z is any group that activates the C.dbd.S double bond
towards a reversible free radical addition fragmentation reaction
and R" is selected from the group consisting of, generally, any
group that can be easily expelled under its free radical form
R'.circle-solid.) upon an addition-fragmentation reaction. This
control agent can be attached to the cellulosic backbone through
either Z or R", however, for ease these groups are discussed below
in terms as if they are not the linking group to the cellulosic
backbone (thus, e.g., alkyl would actually be alkylene). R' is
generally selected from the group consisting of optionally
substituted hydrocarbyl, and heteroatom-containing hydrocarbyl.
More specifically, R" is selected from the group consisting of
optionally substituted alkyl, aryl, alkenyl, alkoxy, heterocyclyl,
alkylthio, amino and polymer chains. And still more specifically,
R" is selected from the group consisting of --CH.sub.2Ph,
--CH(CH.sub.3)CO.sub.2CH.sub.2CH.sub.3,
--CH(CO.sub.2CH.sub.2CH.sub.3).su- b.2, --C(CH.sub.3).sub.2CN,
--CH(Ph)CN and --C(CH.sub.3).sub.2Ph. Z is typically selected from
the group consisting of hydrocarbyl, substituted hydrocarbyl,
heteroatom-containing hydrocarbyl and substituted heteroatom
containing hydrocarbyl. More specifically, Z is selected from the
group consisting of optionally substituted alkyl, aryl, heteroaryl,
amino and alkoxy, and most preferably is selected from the group
consisting of amino and alkoxy. In other embodiments, Z is attached
to C.dbd.S through a carbon atom (dithioesters), a nitrogen atom
(dithiocarbamate), two nitrogen atoms in series (dithiocarbazate),
a sulfur atom (trithiocarbonate) or an oxygen atom
(dithiocarbonate). Specific examples for Z can be found in WO
98/01478, WO 99/35177, WO 99/31144, WO 98/58974, U.S. Pat. No. 6,
153, 705 and U.S. patent application Ser. No. 09/676,267, filed
28Sep., 2000, each of which is incorporated herein by reference.
Particularly preferred control agents of the type in formula II are
those where the control agent is attached through R" and Z is
either, a carbazate, --OCH.sub.2CH.sub.3 or pyrrole attached via
the nitrogen atom. As discussed below, linker molecules can be
present to attach the C.dbd.S group to the cellulose backbone
through Z or R".
[0124] In another embodiment, when the -I-CA embodiment is being
used, the control agent may be a nitroxide radical. Broadly, the
nitroxide radical control agent may be characterized by the general
formula --O--NR.sup.5R.sup.6, wherein each of R.sup.5 and R.sup.6
is independently selected from the group of hydrocarbyl,
substituted hydrocarbyl, heteroatom containing hydrocarbyl and
substituted heteroatom containing hydrocarbyl; and optionally
R.sup.5 and R.sup.6 are joined, together in a ring structure. In a
more specific embodiment, the control agent may be characterized by
the general formula III: 6
[0125] where I is a residue capable of initiating a free radical
polymerisation upon homolytic cleavage of the I-O bond, the I
residue being selected from the group consisting of fragments
derived from a free radical initiator, alkyl, substituted alkyl,
alkoxy, substituted alkoxy, aryl, substituted aryl, and
combinations thereof; X is a moiety that is capable of
destabilizing the control agent on a polymerisation time scale; and
each R.sup.1 and R.sup.2, independently, is selected from the group
consisting of alkyl, substituted alkyl, cycloalkyl, substituted
cycloalkyl, heteroalkyl, heterocycloalkyl, substituted
heterocycloalkyl, aryl, substituted aryl, heteroaryl, substituted
heteroaryl, alkoxy, aryloxy, silyl, boryl, phosphino, amino, thio,
seleno, and combinations thereof; and R.sup.3 is selected from the
group consisting of tertiary alkyl, substituted tertiary alkyl,
aryl, substituted aryl, tertiary cycloalkyl, substituted tertiary
cycloalkyl, tertiary heteroalkyl, tertiary heterocycloalkyl,
substituted tertiary heterocycloalkyl, heteroaryl, substituted
heteroaryl, alkoxy, aryloxy and silyl. Preferably, X is hydrogen.
Synthesis of the types of initiator-control agents in formula III
is disclosed in, for example, Hawker et al, "Development of a
Universal Alkoxyamine for `Living` Free Radical Polymerizations, "
J. Am. Chem. Soc., 1999, 121(16), pp. 3904-3920 and U.S. patent
application Ser. No. 09/520,583, filed Mar. 8, 2000 and
corresponding International Application No. PCT/US00/06176, all of
which are incorporated herein by reference.
[0126] Control Agent Attachment
[0127] In order to attach Y units (e.g., initiator control agents)
to the cellulosic backbone, a linker is typically employed (.e.,
C.dbd.I), designated L in formula I. Linkers are at least dual
functional molecules that will react with either a hydroxyl or
acetyl ester group of the cellulosic backbone; the linker will also
be able to react with a precursor molecule that comprises the Y
unit. Typically, a linker molecule has from 2 to 50 non-hydrogen
atoms. Linkers (L) may be selected from any of the molecules
discussed in this section. Given the molecular weights of the
cellulosic backbone and the grafts or blocks that are being added
to that backbone, the length of the linker molecule may be chosen
to affect or not affect the properties of the graft or block
copolymer. In order to reduce the possibility of affecting the
properties of the final polymer, the size of the linker molecule
may be reduced in some embodiments (e.g., lower molecular weight or
steric bulk).
[0128] In some preferred embodiments of the invention, the control
agent is a thio-carbonylthio derivative with the following
structure Z-C(.dbd.S)--S, with the control agent linked to the
cellulosic material via the Z or S moiety, as discussed above in
association with formula II. For graft copolymers, several
techniques are available to attach the control agent to the sugar
units within the chain backbone.
[0129] In a first embodiment, a di-isocyanate linker is used to
attach the control agent to the cellulosic backbone. Generally, a
bis-isocyanate is reacted with a cellulose ester (having a DS
ranging from about 2.5 to 2.7) together with a catalyst, such as a
catalytic amount of dibutyldilauryl tin. In some preferred
embodiments, the linker is a di-isocyanate compound, having from
8-50 non-hydrogen atoms. Isocyanates are known to react with --OH,
--SH and --NH.sub.2 groups, thereby allowing for effective linking
of the cellulosic backbone with a properly prepared control agent.
Di-isocyanate linkers may be characterized by the general formula:
O.dbd.C.dbd.N--R'--N.dbd.C.dbd.O, wherein R' is selected from the
group consisting of optionally substituted alkyl and aryl. The
pendant NCO groups of the bis-isocyanate are then reacted with an
OH-functional control agent Most preferred di-isocyanate linkers
include isophorone di-isocyanate (IPDI) and
hexamethylene-disocyanate. Other useful di-isocyanate derivatives
can be found in "Isocyanates Building Blocks for Organic Synthesis"
Aldrich commercial leaflet (PO Box 355 Milwaukee, Wis. 53201 USA),
which is incorporated herein by reference. An alternative process
comprises forming the chloroformate derivative through phosgenation
of the residual OH of the cellulose ester, and then reacting the
latter with an hydroxyl (or any other NCO reactive) functional
control agent.
[0130] The following scheme 1 shows an embodiment of this method:
7
[0131] In scheme 1, some embodiments will replace CA with Y, in
order to show where the polymerisation may appear to occur. When a
saponification or hydrolysis step is involved as a final step in
the process (see FIG. 2), then the linkage between the control
agent and the cellulose ester backbone is chosen as to resist the
saponification conditions. Particularly preferred are urethane or
amide linkages that tend to be hydrolytically robust to
saponification or hydrolysis conditions. Some examples of OH
functional control agents are: 8
[0132] Another embodiment for a linker (L) is the direct attachment
of thiocarbonyl-thio control agents to the sugar rings. Generally,
in this process the residual OH groups on the cellulosic backbone
are first activated by either chlorosulfonyl acids (e.g.,
tosylates, mesylates, or triflates) or acid chlorides (e.g.,
para-nitrophenyl chloroformate). Thereafter, the cellulosic
material is treated with the metal salt of the corresponding
thiocarbonyl-thio compound (e.g., dithiocarbonate, dithiocarbamate)
to graft the desired control agents to the cellulosic backbone.
This is shown for example in the following scheme 2. 9
[0133] In scheme 2, Ts refers to "tosylate` and Et refers to
"ethyl`.
[0134] In other preferred embodiments, block copolymers are
prepared, with one of the blocks being the cellulosic material.
Anchoring of the control agent to at least one terminal end portion
of the cellulosic material is achieved selectively at the C-1
anomeric carbon of the terminal sugar unit by either reductive
amination or halogenation.
[0135] In the reductive amination route, the reducing terminal
glucose residue is converted to an amino group by reacting the
cellulosic materials with an excess of the amine or hydroxyamine
together with either sodium borohydride or sodium cyanoborohydride.
Reduction under high pressure of hydrogen with a Nickel Raney
catalyst can also be utilised. Details of these procedures can be
found in Danielson S. et al., Glycoconjugate Journal (1986)
3:363-377; Larm O. et al., Carbohydrate Research, 58(1977) 249-251;
WO 98/15566; and EP 0 725 082, each of which is incorporated herein
by reference. The following scheme 3 presents an example of this
pathway: 10
[0136] An amino reactive control agent is then condensed to the
amine end group. Typical amino reactive groups include isocyanate,
isothiocyanate, epoxy, chlorotriazine, carbonate, activated esters
(such as N-hydrosuccimide esters), and the like. Isocyanate
functional control agents are preferred and one example is given
below in scheme 4: 11
[0137] Scheme 4 shows a pyrrole as Z (from formula II). However,
those of skill in the art will appreciate that other moieties can
be used in this location of the control agent, as discussed above
(e.g. the CA-OH compounds listed above).
[0138] In the halogenation route to attach the control agents to
the terminal end portions of the cellulosic backbone, cellulose
esters are depolymerised in a mixture of HBr and acetic anhydride
in methylene chloride as described by De Oliveira W. et al,
Cellulose, 1994, 1, 77-86, which is incorporated herein by
reference. The terminal glycosyl bromide is then displaced by the
thiocarbonyl-thio salt of the corresponding control agent, as
exemplified in the following scheme 5: 12
[0139] Scheme 5 shows ethoxy as Z (from formula II). However, those
of skill in the art will appreciate that other moieties can be used
in this location of the control agent, as discussed above. This
process typically employs a cellulose triacetate (e.g., a fully
esterified cellulosic material) otherwise side-reactions may occur
during the control agent attachment step, which may lead to
branched polymers. A variant of this process comprises hydrolysing
the bromide into OH; the OH-terminated cellulose ester is then
coupled with an OH reactive control agent such as described
above.
[0140] In each of schemes 1-5, the following formula is employed:
13
[0141] wherein R is selected from the group consisting of hydrogen
or acetate and * refers to either an end or additional sugar units.
Also, schemes that use the "n" designation are referring to the
degree of polymerisation, discussed herein.
[0142] Generally, the polymerisation of the graft segments or
blocks proceeds under polymerisation conditions. Polymerisation
conditions include the ratios of starting materials, temperature,
pressure, atmosphere and reaction time. The atmosphere may be
controlled, with an inert atmosphere being preferred, such as
nitrogen or argon. The molecular weight of the polymer can be
controlled via controlled free radical polymerisation techniques or
by controlling the ratio of monomer to initiator. The reaction
media for these polymerisation reactions is either an organic
solvent or bulk monomer or neat. Polymerisation reaction time may
be in the range of from about 0,5 hours to about 72 hours,
preferably from about 1 hour to about 24 hours and more preferably
from about 2 hours to about 12 hours.
[0143] When the control agent is of formula II, the polymerisation
conditions that may be used include temperatures for polymerisation
typically in the range of from about 20.degree. C. to about
110.degree. C., more preferably in the range of from about
50.degree. C. to about 90.degree. C. and even more preferably in
the range of from about 70.degree. C. to about 85.degree. C. The
atmosphere may be controlled, with an inert atmosphere being
preferred, such as nitrogen or argon. The molecular weight of the
polymer is controlled via adjusting the ratio of monomer to control
agent. Generally, the ratio of monomer to control agent is in the
range of from about 200 to about 800. A free radical initiator is
usually added to the reaction mixture, so as to maintain the
polymerisation rate to an acceptable level. Conversely, a too high
free radical initiator to control agent ratio will favour unwanted
dead polymer formation, namely pure homopolymers or block
copolymers of unknown composition. The molar ratios of free radical
initiator to control agent for polymerisation are typically in the
range of from about 2:1 to about 0.02:1.
[0144] When the control agent is of a nitroxide radical type,
polymerisation conditions include temperatures for polymerisation
typically in the range of from about 80.degree. C. to about
130.degree. C., more preferably in the range of from about
95.degree. C. to about 130.degree. C. and even more preferably in
the range of from about 120.degree. C. to about 130.degree. C.
Generally, the ratio of monomer to initiator is in the range of
from about 200 to about 800.
[0145] Initiators used in the polymerization process with a control
agent (and from which I may be derived) may be known in the art,
Such initiators may be selected from the group consisting of alkyl
peroxides, substituted alkyl peroxides, aryl peroxides, substituted
aryl peroxides, acyl peroxides, alkyl hydroperoxides, substituted
alkyl hydroperoxides, aryl hydroperoxides, substituted aryl
hydroperoxides, heteroalkyl peroxides, substituted heteroalkyl
peroxides, heteroalkyl hydroperoxides, substituted heteroalkyl
hydroperoxides, heteroaryl peroxides, substituted heteroaryl
peroxides, heteroaryl hydroperoxides, substituted heteroaryl
hydroperoxides, alkyl peresters, substituted alkyl peresters, aryl
peresters, substituted aryl peresters, and azo compounds. Specific
initiators include BPO and AIBN. In some embodiments, as discussed
above, the I fragment or residue may be selected from the group
consisting of fragments derived from a free radical initiator,
alkyl, substituted alkyl, alkoxy, substituted alkoxy, aryl,
substituted aryl, and combinations thereof. Different I fragments
may be preferred depending on the embodiment of this invention
being practised. For example, when the di-thio control agents as
generally described in formula II are employed for Y equal to
-I-CA, the I fragment may be considered to be a portion of the
linker, for example, may be considered to be --CH(COOR.sup.10)--
where R.sup.10 is selected from the group consisting of hydrocarbyl
and substituted hydrocarbyl, and more specifically alkyl and
substituted alkyl. Initiation may also be by heat or radiation, as
is generally known in the art.
[0146] Ideally, the growth of grafts or blocks attached to the
cellulosic backbone occurs with high conversion. Conversions are
determined by NMR via integration of polymer to monomer signals.
Conversions may also be determined by size exclusion chromatography
(SEC) via integration of polymer to monomer peak. For UV detection,
the polymer response factor must be determined for each
polymer/monomer polymerisation mixture. Typical conversions can be
50% to 100%, more specifically in the range of from about 60% to
about 90%.
[0147] Optionally, the dithio moiety of the control agent of those
in formula II can be cleaved by chemical or thermal ways, if one
wants to reduce the sulfur content of the polymer and prevent any
problems associated with presence of the control agents chain ends,
such as odour or discolouration. Typical chemical treatment
includes the catalytic or stoichiometric addition of base such as a
primary amine, acid or anhydride, or oxidising agents such as
hypochloride salts.
[0148] As used herein, "block copolymer" refers to a polymer
comprising at least two segments having at least two differing
compositions, where the monomers are not incorporated into the
polymer architecture in a solely statistical or uncontrolled
manner. In this invention, at least one of the blocks is a
cellulosic block. Although there may be two, three, four or more
monomers in a single block-type polymer architecture, it will still
be referred to herein as a block copolymer. The block copolymers of
this invention may include one or more blocks of random copolymer
(sometimes referred to herein as an "R" block) together with one or
more blocks of single monomers, so long as there is a cellulosic
backbone from which the blocks are centrally tied. Moreover, the
random block can vary in composition or size with respect to the
overall block copolymer. In some embodiments, for example, the
random block will account for between 5 and 80% by weight of the
mass of the block copolymer. In other embodiments, the random block
R will account for more or less of the mass of the block copolymer,
depending on the application. Furthermore, the random block may
have a compositional gradient of one monomer to the other (e.g.,
A:B) that varies across the random block in an algorithmic fashion,
with such algorithm being either linear having a desired slope,
exponential having a desired exponent (such as a number from 0.1-5)
or logarithmic. The random block may be subject to the same kinetic
effects, such as composition drift, that would be present in any
other radical copolymerisation and its composition, and size may be
affected by such kinetics, such as Markov kinetics.
[0149] A "block" within the scope of the block copolymers of this
invention typically comprises about 5 or more monomers of a single
type (with the random blocks being defined by composition and/or
weight percent, as described above). In preferred embodiments, the
number of monomers within a single block may be about 10 or more,
about 15 or more, about 20 or more or about 50 or more. The
existence of a block copolymer according to this invention is
determined by methods known to those of skill in the art. For
example, those of skill in the art may consider nuclear magnetic
resonance (NMR) studies, measured increase of molecular weight upon
addition of a second monomer to chain-extend a first block,
observation of microphase separation, including long range order
(determined by X-ray diffraction), microscopy and/or birefringence
measurements. Other methods of determining the presence of a block
copolymer include mechanical property measurements, (e.g.,
elasticity of hard/soft/hard block copolymers), thermal analysis
and gradient elution chromatography (e.g., absence of
homopolymer).
[0150] The graft(s) or additional block(s) attached to the
cellulosic backbone typically has a number average molecular weight
of from 100 to 10,000,000 Da (preferably from 2,000 to 200,000 Da,
more preferably from 10,000 to 100,000 Da) and a weight average
molecular weight of from 150 to 20,000,000 Da (preferably from
5,000 to 450,000 Da, more preferably from 20,000 to 400,000
Da).
[0151] The monomers chosen for the grafts or blocks are typically
selected in a manner so as to produce the desired effect on the
surface or fibre. For example, the monomers may be chosen for their
particular hydrophilic or hydrophobic characteristics.
[0152] Hydrophilic monomers include, but are not limited to,
acrylic acid, methacrylic acid, N,N-dimethylacrylamide, dimethyl
aminoethyl methacrylate, quaternised dimethylaminoethyl
methacrylate, methacrylamide, N-t-butyl acrylamide, maleic acid,
maleic anhydride and its half esters, crotonic acid, itaconic acid,
acrylamide, acrylate alcohols, hydroxyethyl methacrylate,
diallyldimethyl ammonium chloride, vinyl ethers (such as methyl
vinyl ether), maleimides, vinyl pyridine; vinyl imidazole, other
polar vinyl heterocyclics, styrene sulfonate, allyl alcohol, vinyl
alcohol (such as that produced by the hydrolysis of vinyl acetate
after polymerisation), salts of any acids and amines listed above,
and mixtures thereof. Preferred hydrophilic monomers include
acrylic acid, N,N-dimethyl acrylamide, dimethylaminoethyl
methacrylate, quaternized dimethyl aminoethyl methacrylate, vinyl
pyrrolidone, salts of acids and amines listed above, and
combinations thereof.
[0153] Hydrophobic monomers may be listed above and include, but
are not limited to, acrylic or methacrylic acid esters of
C.sub.1-C.sub.18 alcohols, such as methanol, ethanol, methoxy
ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol,
1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol,
1-methyl-1-butanol, 3-methyl-1-butanol, 1-methyl-1-pentanol,
2-methyl-1-pentanol, 3-methyl-1-pentanol, t-butanol
(2-methyl-2-propanol), cyclohexanol, neodecanol, 2-ethyl-1-butanol,
3-heptanol, benzyl alcohol, 2-octanol, 6-methyl-1-heptanol,
2-ethyl-1-hexanol; 3,5 dimethyl-1-hexanol,
3,5,5,-tri-methyl-1hexanol, 1-decanol, 1-dodecanol; 1-hexadecanol,
1-octadecanol, and the like, the alcohols having from about 1 to
about 18 carbon atoms, preferably from about 1 to about 12 carbon
atoms; styrene; polystyrene macromer, vinyl acetate; vinyl
chloride; vinylidene chloride; vinyl propionate;
alpha-methylstyrene; t-butylstyrene; butadiene; cyclohexadiene;
ethylene; propylene; vinyl toluene; and mixtures thereof. Preferred
hydrophobic monomers include n-butyl methacrylate, isobutyl
methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-ethylhexyl
methacrylate, methyl methacrylate, vinyl acetate, vinyl acetamide,
vinyl formamide, and mixtures thereof, more preferably t-butyl
acrylate, t-butyl methacrylate, or combinations thereof.
[0154] The cellulosic graft or copolymers of this invention may
have properties that can be tuned or controlled depending on the
desired use of the polymer. Thus, for example, when the water
solubility of the chosen graft material is low or poor and the
cellulosic backbone is more water soluble than the grafts (e.g., is
cellulose mono-acetate), then the polymer may form micelle like
structures, with the hydrophobic materials being attracted to each
other and the more hydrophilic materials forming an outer ring.
[0155] Following the above procedures yields a polymer either
having a cellulosic backbone with grafts of controlled structure
and composition or a block copolymer or a combination of both. In
some embodiments the polymers obtained are novel, which may be
characterised by the size of the celluosic backbone, the number of
graft chains extending from the backbone and the length of the
graft chains. In addition, these grafts are preferably single point
attached to the backbone, and in some embodiments preferably,
water-soluble. Where control of the polymerisation is partially
list, then some of the grafts may be connected to several backbone
chains leading to cross-linking. Water solubility is defined above.
Cross-linking may be determined for the polymers of this
application by light scattering or more specifically dynamic light
scattering (DLS). Alternatively, filtration of the polymer sample
though an about 0.2 to 0.5 micron filter without inducing a
backpressure would, for purposes of this application, indicate a
lack of cross-linking in the polymer sample. Also alternatively,
other mechanical methods of determining cross-linking may be used,
which are known to those of skill in the art. If a polymer passes
any of these tests, it is considered substantially free of
cross-linking for the purposes of this application, with
"substantially" meaning less than or equal to about 20%
cross-linked.
[0156] Using the above-described parameters, the novel polymers of
this application are cellulosic backboned graft polymers which have
a degree of substitution (DS) of grafts in the bulk sample in the
range of from 0.02 to about 0.15. As discussed above, the DS of
graft chains in the bulk sample is dependant on two factors, the
length of the cellulosic backbone and number of grafts. Generally,
to fit the preferred DS, the cellulosic backbone typically has a
molecular weight in the range of from about 10,000 to about 40,000
and the number of grafts can range from about 3 to 12. The general
calculation to determine these numbers is that the molecular weight
(e.g., either number average or weight average) of the cellulosic
backbone is divided by the molecular weight of each sugar unit.
This yields the number of sugar units, which is then multiplied by
the degree of substitution in the bulk sample to yield number of
grafts per cellulosic backbone. In formula form, this is {(Mw
backbone/Mw sugar unit).times.DS}=number of grafts. The grafts on
the cellulosic backbone have a length (i.e., degree of
polymerisation) of between 25 and 200 monomer units and more
preferably between 50 and 100 monomer units.
[0157] The cellulosic backbone is most preferably cellulose
monoacetate, but the other cellulosic backbones are not excluded.
The grafts can be selected from any of the above-listed monomers
and depend on the end use of the polymer. As shown in the examples,
the polymers that have this structure tend to have properties that
allow for improved adsorption to surface and fibres.
[0158] It should be noted that, although the polymer and its
synthesis have been described by reference to polymers having a
cellulosic backbone, the properties and techniques described are
equally applicable to polymers having a different polysaccharide
backbone.
[0159] Compositions
[0160] The graft and copolymers of this invention provide benefits
to fibres such as cotton, and other substrates by adhering to the
surface during an aqueous treatment process. The level of
adsorbancy can be adjusted with the selection of monomers, the
graft density and the graft length. The grafts or co-blocks also
determine the type of benefit added to the fibre or surface.
[0161] Surfactants
[0162] Compositions according to the first aspect of the invention
must also comprise one or more surfactants suitable for use in
laundry cleaning, that is, laundry wash and/or rinsing, products.
In the most general sense, these may be chosen from one or more of
soap and non-soap anionic, cationic, nonionic, amphoteric and
zwitterionic surface-active compounds and mixtures thereof. Many
suitable surface-active compounds are available and are fully
described in the literature, for example, in "Surface-Active Agents
and Detergents", Volumes I and II, by Schwartz, Perry and
Berch.
[0163] For those compositions intended as laundry wash products,
preferably, the surfactant(s) is/are selected from one or more
soaps and synthetic non-soap anionic and non-ionic compounds.
Detergent compositions suitable for use in most automatic fabric
washing machines generally contain anionic non-soap surfactant, or
non-ionic surfactant, or combinations of the two in any suitable
ratio, optionally together with soap.
[0164] For example, laundry wash compositions of the invention may
contain linear alkylbenzene sulphonate anionic surfactants,
particularly linear alkylbenzene sulphonates having an alkyl chain
length of C.sub.8-C.sub.15. It is preferred if the level of linear
alkylbenzene sulphonate is from 0 wt % to 30 wt %, more preferably
1 wt % to 25 wt %, most preferably from 2 wt % to 15 wt %.
[0165] The laundry wash compositions of the invention may
additionally or alternatively contain one or more other anionic
surfactants in total amounts corresponding to percentages quoted
above for alkyl benzene sulphonates. Suitable anionic surfactants
are well-known to those skilled in the art. These include primary
and secondary alkyl sulphates, particularly C.sub.8-C.sub.15
primary alkyl sulphates; alkyl ether sulphates; olefin sulphonates;
alkyl xylene sulphonates; dialkyl sulphosuccinates; and fatty acid
ester sulphonates. Sodium salts are generally preferred.
[0166] The laundry wash compositions of the invention may contain
non-ionic surfactant. Nonionic surfactants that may be used include
the primary and secondary alcohol ethoxylates, especially the
C.sub.8-C.sub.20 aliphatic alcohols ethoxylated with an average of
from 1 to 20 moles of ethylene oxide per mole of alcohol, and more
especially the C.sub.10-C.sub.15 primary and secondary aliphatic
alcohols ethoxylated with an average of from 1 to 10 moles of
ethylene oxide per mole of alcohol. Non-ethoxylated nonionic
surfactants include alkylpolyglycosides, glycerol monoethers, and
polyhydroxyamides (glucamide).
[0167] It is preferred if the level of total non-ionic surfactant
is from 0 wt % to 30 wt %, preferably from 1 wt/o to 25 wt %, most
preferably from 2 wt % to 15 wt %.
[0168] Another class of suitable surfactants comprises certain
mono-long chain-alkyl cationic surfactants for use in main-wash
laundry compositions according to the invention. Cationic
surfactants of this type include quaternary ammonium salts of the
general formula R.sub.1R.sub.2R.sub.3R.sub.4N.sup.+X.sup.- wherein
the R groups are long or short hydrocarbon chains, typically alkyl,
hydroxyalkyl or ethoxylated alkyl groups, and X is a counter-ion
(for example, compounds in which R.sub.1 is a C.sub.8-C.sub.22
alkyl group, preferably a C.sub.8-C.sub.10 or C.sub.12-C.sub.14
alkyl group, R.sub.2 is a methyl group, and R.sub.3 and R.sub.4,
which may be the same or different, are methyl or hydroxyethyl
groups); and cationic esters (for example, choline esters).
[0169] The choice of surface-active compound (surfactant), and the
amount present in the laundry wash compositions according to the
invention, will depend on the intended use of the detergent
composition. In fabric washing compositions, different surfactant
systems may be chosen, as is well known to the skilled formulator,
for handwashing products and for products intended for use in
different types of washing machine. The total amount of surfactant
present will also depend on the intended end use and may be as high
as 60 wt %, for example, in a composition for washing fabrics by
hand. In compositions for machine washing of fabrics, an amount of
from 5 to 40 wt % is generally appropriate. Typically the
compositions will comprise at least 2 wt % surfactant e.g. 2-60%,
preferably 15-40% most preferably 25-35%.
[0170] In the case of laundry rinse compositions according to the
invention the surfactant(s) is/are preferably selected from fabric
conditioning agents. In fact, conventional fabric conditioning
agent may be used. These conditioning agents may be cationic or
non-ionic. If the fabric conditioning compound is to be employed in
a main wash detergent composition the compound will typically be
non-ionic. If used in the rinse phase, they will typically be
cationic. They may for example be used in amounts from 0.5% to 35%,
preferably from 1% to 30% more preferably from 3% to 25% by weight
of the composition.
[0171] Preferably the fabric conditioning agent(s) have two long
chain alkyl or alkenyl chains each having an average chain length
greater than or equal to C.sub.16. Most preferably at least 50% of
the long chain alkyl or alkenyl groups have a chain length of
C.sub.18 or above. It is preferred if the long chain alkyl or
alkenyl groups of the fabric conditioning agents are predominantly
linear.
[0172] The fabric conditioning agents are preferably compounds that
provide excellent softening, and are characterised by a chain
melting L.beta. to L.alpha. transition temperature greater than
25.degree. C., preferably greater than 35.degree. C., most
preferably greater than 45.degree. C. This L.beta. to L.alpha.
transition can be measured by DSC as defined in "Handbook of Lipid
Bilayers, D Marsh, CRC Press, Boca Raton, Fla., 1990 (pages 137 and
337).
[0173] Substantially insoluble fabric conditioning compounds in the
context of this invention are defined as fabric conditioning
compounds having a solubility less than 1.times.10.sup.-3 wt % in
demineralised water at 20.degree. C. Preferably the fabric
softening compounds have a solubility less than 1.times.10.sup.-4
wt %, most preferably less than 1.times.10.sup.-8 to
1.times.10.sup.-6. Preferred cationic fabric softening agents
comprise a substantially water insoluble quaternary ammonium
material comprising a single alkyl or alkenyl long chain having an
average chain length greater than or equal to C.sub.20 or, more
preferably, a compound comprising a polar head group and two alkyl
or alkenyl chains having an average chain length greater than or
equal to C.sub.14.
[0174] Preferably, the cationic fabric softening agent is a
quaternary ammonium material or a quaternary ammonium material
containing at least one ester group. The quaternary ammonium
compounds containing at least one ester group are referred to
herein as ester-linked quaternary ammonium compounds.
[0175] As used in the context of the quarternary ammonium cationic
fabric softening agents, the term `ester group`, includes an ester
group which is a linking group in the molecule.
[0176] It is preferred for the ester-linked quaternary ammonium
compounds to contain two or more ester groups. In both monoester
and the diester quaternary ammonium compounds it is preferred if
the ester group(s) is a linking group between the nitrogen atom and
an alkyl group. The ester groups(s) are preferably attached to the
nitrogen atom via another hydrocarbyl group.
[0177] Also preferred are quaternary ammonium compounds containing
at least one ester group, preferably two, wherein at least one
higher molecular weight group containing at least one ester group
and two or three lower molecular weight groups are linked to a
common nitrogen atom to produce a cation and wherein the
electrically balancing anion is a halide, acetate or lower
alkosulphate ion, such as chloride or methosulphate. The higher
molecular weight substituent on the nitrogen is preferably a higher
alkyl group, containing 12 to 28, preferably 12 to 22, e.g. 12 to
20 carbon atoms, such as coco-alkyl, tallowalkyl, hydrogenated
tallowalkyl or substituted higher alkyl, and the lower molecular
weight substituents are preferably lower alkyl of 1 to 4 carbon
atoms, such as methyl or ethyl, or substituted lower alkyl. One or
more of the said lower molecular weight substituents may include an
aryl moiety or may be replaced by an aryl, such as benzyl, phenyl
or other suitable substituents.
[0178] Preferably the quaternary ammonium material is a compound
having two C.sub.12-C.sub.22 alkyl or alkenyl groups connected to a
quaternary ammonium head group via at least one ester link,
preferably two ester links or a compound comprising a single long
chain with an average chain length equal to or greater than
C.sub.20.
[0179] More preferably, the quaternary ammonium material comprises
a compound having two long chain alkyl or alkenyl chains with an
average chain length equal to or greater than C.sub.14. Even more
preferably each chain has an average chain length equal to or
greater than C.sub.16. Most preferably at least 50% of each long
chain alkyl or alkenyl group has a chain length of C.sub.18. It is
preferred if the long chain alkyl or alkenyl groups are
predominantly linear.
[0180] The most preferred type of ester-linked quaternary ammonium
material that can be used in laundry rinse compositions according
to the invention is represented by the formula (B): 14
[0181] wherein T is 15
[0182] each R.sup.20 group is independently selected from C.sub.1-4
alkyl, hydroxyalkyl or C.sub.2-4 alkenyl groups; and wherein each
R.sup.21 group is independently selected from C.sub.8-28 alkyl or
alkenyl groups; Q.sup.- is any suitable counter-ion, i.e. a halide,
acetate or lower alkosulphate ion, such as chloride or
methosulphate;
[0183] w is an integer from 1-5 or is 0; and
[0184] y is an integer from 1-5.
[0185] It is especially preferred that each R.sup.20 group is
methyl and w is 1 or 2.
[0186] It is advantageous for environmental reasons if the
quaternary ammonium material is biologically degradable.
[0187] Preferred materials of this class such as 1,2-bis[hardened
tallowoyloxy]-3-trimethylammonium propane chloride and their method
of preparation are, for example, described in U.S. Pat. No.
4,137,180. Preferably these materials comprise small amounts of the
corresponding monoester as described in U.S. Pat. No. 4,137,180 for
example 1-hardened tallowoyloxy-2-hydroxy-3-trimethylammonium
propane chloride.
[0188] Another class of preferred ester-linked quaternary ammonium
materials for use in laundry rinse compositions according to the
invention can be represented by the formula: 16
[0189] wherein T is 17
[0190] and
[0191] wherein R.sup.20, R.sup.21, w, and Q.sup.- are as defined
above.
[0192] Of the compounds of formula (C),
di-(tallowyloxyethyl)-dimethyl ammonium chloride, available from
Hoechst, is the most preferred. Di-(hardened
tallowyloxyethyl)dimethyl ammonium chloride, ex Hoechst and
di-(tallowyloxyethyl)-methyl hydroxyethyl methosulphate are also
preferred.
[0193] Another preferred class of quaternary ammonium cationic
fabric softening agent is defined by formula (D): 18
[0194] where R.sup.20, R.sup.21 and Q.sup.- are as hereinbefore
defined.
[0195] A preferred material of formula (D) is di-hardened
tallow-diethyl ammonium chloride, sold under the Trademark Arquad
2HT.
[0196] The optionally ester-linked quaternary ammonium material may
contain optional additional components, as known in the art, in
particular, low molecular weight solvents, for instance isopropanol
and/or ethanol, and co-actives such as nonionic softeners, for
example fatty acid or sorbitan esters.
[0197] Detergency Builders
[0198] The compositions of the invention, when used as laundry wash
compositions, will generally also contain one or more detergency
builders. The total amount of detergency builder in the
compositions will typically range from 5 to 80 wt %, preferably
from 10 to 60 wt %.
[0199] Inorganic builders that may be present include sodium
carbonate, if desired in combination with a crystallisation seed
for calcium carbonate, as disclosed in GB 1 437 950 (Unilever);
crystalline and amorphous aluminosilicates, for example, zeolites
as disclosed in GB 1 473 201 (Henkel), amorphous aluminosilicates
as disclosed in GB 1 473 202 (Henkel) and mixed
crystalline/amorphous aluminosilicates as disclosed in GB 1 470 250
(Procter & Gamble); and layered silicates as disclosed in EP
164 514B (Hoechst). Inorganic phosphate builders, for example,
sodium orthophosphate, pyrophosphate and tripolyphosphate are also
suitable for use with this invention.
[0200] The compositions of the invention preferably contain an
alkali metal, preferably sodium, aluminosilicate builder. Sodium
aluminosilicates may generally be incorporated in amounts of from
10 to 70% by weight (anhydrous basis), preferably from 25 to 50 wt
%.
[0201] The alkali metal aluminosilicate may be either crystalline
or amorphous or mixtures thereof, having the general formula:
0.8-1.5 Na.sub.2O. Al.sub.2O.sub.3. 0.8-6 SiO.sub.2.
[0202] These materials contain some bound water and are required to
have a calcium ion exchange capacity of at least 50 mg CaO/g. The
preferred sodium aluminosilicates contain 1.5-3.5 SiO.sub.2 units
(in the formula above). Both the amorphous and the crystalline
materials can be prepared readily by reaction between sodium
silicate and sodium aluminate, as amply described in the
literature. Suitable crystalline sodium aluminosilicate
ion-exchange detergency builders are described, for example, in GB
1 429 143 (Procter & Gamble). The preferred sodium
aluminosilicates of this type are the well-known commercially
available zeolites A and X, and mixtures thereof.
[0203] The zeolite may be the commercially available zeolite 4A now
widely used in laundry detergent powders. However, according to a
preferred embodiment of the invention, the zeolite builder
incorporated in the compositions of the invention is maximum
aluminium zeolite P (zeolite MAP) as described and claimed in EP
384 070A (Unilever). Zeolite MAP is defined as an alkali metal
aluminosilicate of the zeolite P type having a silicon to aluminium
ratio not exceeding 1.33, preferably within the range of from 0.90
to 1.33, and more preferably within the range of from 0.90 to
1.20.
[0204] Especially preferred is zeolite MAP having a silicon to
aluminium ratio not exceeding 1.07, more preferably about 1.00. The
calcium binding capacity of zeolite MAP is generally at least 150
mg CaO per g of anhydrous material.
[0205] Organic builders that may be present include polycarboxylate
polymers such as polyacrylates, acrylic/maleic copolymers, and
acrylic phosphinates; monomeric polycarboxylates such as citrates,
gluconates, oxydisuccinates, glycerol mono-, di and trisuccinates,
carboxymethyloxy succinates, carboxymethyloxymalonates,
dipicolinates, hydroxyethyliminodiacetates, alkyl- and
alkenylmalonates and succinates; and sulphonated fatty acid salts.
This list is not intended to be exhaustive.
[0206] Especially preferred organic builders are citrates, suitably
used in amounts of from 5 to 30 wt %, preferably from 10 to 25 wt
%; and acrylic polymers, more especially acrylic/maleic copolymers,
suitably used in amounts of from 0.5 to 15 wt %, preferably from 1
to 10 wt %.
[0207] Builders, both inorganic and organic, are preferably present
in alkali metal salt, especially sodium, salt, form.
[0208] Bleaches
[0209] Laundry wash compositions according to the invention may
also suitably contain a bleach system. Fabric washing compositions
may desirably contain peroxy bleach compounds, for example,
inorganic persalts or organic peroxyacids, capable of yielding
hydrogen peroxide in aqueous solution.
[0210] Suitable peroxy bleach compounds include organic peroxides
such as urea peroxide, and inorganic persalts such as the alkali
metal perborates, percarbonates, perphosphates, persilicates and
persulphates. Preferred inorganic persalts are sodium perborate
monohydrate and tetrahydrate, and sodium percarbonate.
[0211] Especially preferred is sodium percarbonate having a
protective coating against destabilisation by moisture. Sodium
percarbonate having a protective coating comprising sodium
metaborate and sodium silicate is disclosed in GB 2 123 044B
(Kao).
[0212] The peroxy bleach compound is suitably present in an amount
of from 0.1 to 35 wt %, preferably from 0.5 to 25 wt %. The peroxy
bleach compound may be used in conjunction with a bleach activator
(bleach precursor) to improve bleaching action at low wash
temperatures. The bleach precursor is suitably present in an amount
of from 0.1 to 8 wt %, preferably from 0.5 to 5 wt %.
[0213] Preferred bleach precursors are peroxycarboxylic acid
precursors, more especially peracetic acid precursors and
pernonanoic acid precursors. Especially preferred bleach precursors
suitable for use in the present invention are N,N,N',N',-tetracetyl
ethylenediamine (TAED) and sodium nonanoyloxybenzene sulphonate.
(SNOBS). The novel quaternary ammonium and phosphonium bleach
precursors disclosed in U.S. Pat. No. 4,751,015 and U.S. Pat. No.
4,818,426 (Lever Brothers Company) and EP 402 971A (Unilever), and
the cationic bleach precursors disclosed in EP 284 292A and EP 303
520A (Kao) are also of interest.
[0214] The bleach system can be either supplemented with or
replaced by a peroxyacid examples of such peracids can be found in
U.S. Pat. No. 4,686,063 and U.S. Pat. No. 5,397,501 (Unilever). A
preferred example is the imido peroxycarboxylic class of peracids
described in EP A 325 288, EP A 349 940, DE 382 3172 and EP 325
289. A particularly preferred example is phthalimido peroxy caproic
acid (PAP). Such peracids are suitably present at 0.1-12%,
preferably 0.5-10%.
[0215] A bleach stabiliser (transition metal sequestrant) may also
be present. Suitable bleach stabilisers include ethylenediamine
tetra-acetate (EDTA), the polyphosphonates such as Dequest (Trade
Mark) and non-phosphate stabilisers such as EDDS (ethylene diamine
di-succinic acid). These bleach stabilisers are also useful for
stain removal especially in products containing low levels of
bleaching species or no bleaching species.
[0216] An especially preferred bleach system comprises a peroxy
bleach compound (preferably sodium percarbonate optionally together
with a bleach activator), and a transition metal bleach catalyst as
described and claimed in EP 458 397A, EP 458 398A and EP 509 787A
(Unilever).
[0217] Enzymes
[0218] Laundry wash compositions according to the invention may
also contain one or more enzyme(s). Suitable enzymes include the
proteases, amylases, cellulases, oxidases, peroxidases and lipases
usable for incorporation in detergent compositions. Preferred
proteolytic enzymes (proteases) are catalytically active protein
materials which degrade or alter protein types of stains when
present as in fabric stains in a hydrolysis reaction. They may be
of any suitable origin, such as vegetable, animal, bacterial or
yeast origin.
[0219] Proteolytic enzymes or proteases of various qualities and
origins and having activity in various pH ranges of from 4-12 are
available and can be used in the instant invention. Examples of
suitable proteolytic enzymes are the subtilisins which are obtained
from particular strains of B. Subtilis B. licheniformis, such as
the commercially available subtilisins Maxatase (Trade Mark), as
supplied by Gist Brocades N. V., Delft, Holland, and Alcalase
(Trade Mark), as supplied by Novo Industri A/S, Copenhagen,
Denmark.
[0220] Particularly suitable is a protease obtained from a strain
of Bacillus having maximum activity throughout the pH range of
8-12, being commercially available, e.g. from Novo Industri A/S
under the registered trade-names Esperase (Trade Mark) and Savinase
(Trade-Mark). The preparation of these and analogous enzymes is
described in GB 1 243 785. Other commercial proteases are Kazusase
(Trade Mark obtainable from Showa-Denko of Japan), Optimase (Trade
Mark from Miles Kali-Chemie, Hannover, West Germany), and Superase
(Trade Mark obtainable from Pfizer of U.S.A.).
[0221] Detergency enzymes are commonly employed in granular form in
amounts of from about 0.1 to about 3.0 wt %. However, any suitable
physical form of enzyme may be used.
[0222] Other Optional Ingredients
[0223] The compositions of the invention may contain alkali metal,
preferably sodium carbonate, in order to increase detergency and
ease processing. Sodium carbonate may suitably be present in
amounts ranging from 1 to 60 wt %, preferably from 2 to 40 wt %.
However, compositions containing little or no sodium carbonate are
also within the scope of the invention.
[0224] Powder flow may be improved by the incorporation of a small
amount of a powder structurant, for example, a fatty acid (or fatty
acid soap), a sugar, an acrylate or acrylate/maleate copolymer, or
sodium silicate. One preferred powder structurant is fatty acid
soap, suitably present in an amount of from 1 to 5 wt %.
[0225] Yet other materials that may be present in detergent
compositions of the invention include sodium silicate;
antiredeposition agents such as cellulosic polymers; inorganic
salts such as sodium sulphate; lather control agents or lather
boosters as appropriate; proteolytic and lipolytic enzymes; dyes;
coloured speckles; perfumes; foam controllers; fluorescers and
decoupling polymers. This list it hot intended to be
exhaustive.
[0226] It is often advantageous if soil release or soil suspending
polymers are present, for example in amounts in the order of 0.01%
to 10%, preferably in the order of 0.1% to 5% and in particular in
the order of 0.2% to 3% by weight, such as
[0227] cellulose derivatives such as cellulose hydroxyethers,
methyl cellulose, ethyl cellulose, hydroxypropyl methyl cellulose,
hydroxybutyl methyl cellulose;
[0228] polyvinyl esters grafted onto polyalkylene backbones, such
as polyvinyl acetates grafted onto polyoxyethylene backbones
(EP-A-219 048);
[0229] polyvinyl alcohols;
[0230] polyester copolymers based on ethylene terephthalate and/or
propylene terephthalate units and polyethyleneoxy terephthalate
units, with a molar ratio (number of units) of ethylene
terephthalate and/or propylene terephthalate/(number of units)
polyethyleneoxy terephthalate in the order of 1/10 to 10/1, the
polyethyleneoxy terephthalate units having polyethyleneoxy units
with a molecular weight in the order of 300 to 10,000, with a
molecular weight of the copolyester in the order of 1000 to
100,000;
[0231] polyester copolymers based on ethylene terephthalate and/or
propylene terephthalate units and polyethyleneoxy and/or
polypropyleneoxy units, with a molar ratio (number of units) of
ethylene terephthalate and/or propylene terephthalate/(number of
units) polyethyleneoxy and/or polypropyleneoxy in the order of 1/10
to 10/1, the polyethyleneoxy and/or polypropyleneoxy units having a
molecular weight in the order of 250 to 10,000, with a molecular
weight of the copolyester in the order of 1000 to 100,000 (U.S.
Pat. No. 3,959,230, U.S. Pat. No. 3,962,152, U.S. Pat. No.
3,893,929, U.S. Pat. No. 4,116,896, U.S. Pat. No. 4,702,857, U.S.
Pat. No. 4,770,666, EP-A-253 567, EP-A-201-124);
[0232] copolymers of ethylene or propylene terephthalate
/polyethyleneoxy terephthalate comprising sulphoisophthaloyl units
in their chain (U.S. Pat. No. 4,711,730, U.S. Pat. No. 4,702,857,
U.S. Pat. No. 4,713,194);
[0233] terephthalic copolyester oligomers having
polyalkyleneoxyalkyl sulphonate/sulphoaroyl terminal groups and
optionally containing sulphoisophthaloyl units in their chain (U.S.
Pat. No. 4,721,580, U.S. Pat. No. 5,415,807, U.S. Pat. No.
4,877,896, U.S. Pat. No. 5,182,043, U.S. Pat. No, 5,599,782, U.S.
Pat. No. 4,764,289, EP-A-311 342, WO92/04433, WO97/42293);
[0234] sulphonated terephthalic copolyesters with a molecular
weight less than 20,000, obtained e.g. from a diester of
terephthalic acid, isophthalic acid, a diester of sulphoisophthalic
acid and a diol, in particular ethylene glycol (WO95/32997);
[0235] polyurethane polyesters, obtained by reaction of a polyester
with a molecular weight of 300 to 4000, obtained from a
terephthalic acid diester, possibly a sulphoisophthalic acid
diester and a diol, on a prepolymer with isocyanate terminal
groups, obtained from a polyethyleneoxy glycol with a molecular
weight of 600 to 4000 and a diisocyanate (U.S. Pat. No.
4,201,824);
[0236] sulphonated polyester oligomers obtained by sulphonation of
an oligomer derived from ethoxylated allyl alcohol, dimethyl
terephthalate and 1,2-propylene diol, having 1 to 4 sulphonate
groups (U.S. Pat. No. 4,968,451).
[0237] Use
[0238] The composition when diluted in the wash liquor (during a
typical wash cycle) will typically give a pH of the wash liquor
from 7 to 11, preferably from 7 to 10.5, for a wash product.
Treatment of a fabric with a soil-release polymer in accordance
with a preferred version of the second aspect of the present
invention can be made by any suitable method such as washing,
soaking or rinsing.
[0239] Typically the treatment will involve a washing or rinsing
method such as treatment in the main wash or rinse cycle of a
washing machine and involves contacting the fabric with an aqueous
medium comprising the composition according to the first aspect of
the present invention.
[0240] Product Form
[0241] Compositions according to the first aspect of the present
invention may be formulated in any convenient form, for example as
powders, liquids (aqueous or non-aqueous) or tablets. When the
compositions are liquids, they may also be provided in encapsulated
unit-dose form.
[0242] Particulate detergent compositions are suitably prepared by
spray-drying a slurry of compatible heat-insensitive ingredients,
and then spraying on or post-dosing those ingredients unsuitable
for processing via the slurry. The skilled detergent formulator
will have no difficulty in deciding which ingredients should be
included in the slurry and which should not.
[0243] Particulate detergent compositions of the invention
preferably have a bulk density of at least 400 g/l, more preferably
at least 500 gl. Especially preferred compositions have bulk
densities of at least 650 g/litre, more preferably at least 700
g/litre.
[0244] Such powders may be prepared either by post-tower
densification of spray-dried powder, or by wholly non-tower methods
such as dry mixing and granulation; in both cases a high-speed
mixer/granulator may advantageously be used. Processes using
high-speed mixer/granulators are disclosed, for example, in EP 340
013A, EP 367 339A, EP 390 251A and EP 420 317A (Unilever).
[0245] Liquid detergent compositions can be prepared by admixing
the essential and optional ingredients thereof in any desired order
to provide compositions containing components in the requisite
concentrations. Liquid compositions according to the present
invention can also be in compact form which means it will contain a
lower level of water compared to a conventional liquid
detergent.
[0246] The present invention will now be explained in more detail
by way of the following non-limiting examples.
EXAMPLES
[0247] General
[0248] In the examples of this invention, syntheses in inert
atmospheres were carried out under a nitrogen or argon atmosphere.
Other chemicals were purchased from commercial sources and used as
received, except for monomers, which were filtered through a short
column of basic aluminum oxide to remove the inhibitor and degassed
by applying vacuum. Size Exclusion Chromatography was performed
using automated rapid GPC system. In the current setup
N,N-dimethylformamide containing 0.1% of trifluoroacetic acid was
used as an eluant and polystyrene-based columns. All of the
molecular weight results obtained are relative to linear
polystyrene standards. .sup.1H NMR was carried out using a Bruker
spectrometer (300 MHz) with CDCl.sub.3 (chloroform-d) as
solvent.
[0249] A. Preparation of Polymers
Example 1
Preparation of Grafted Polymers
[0250] Parts A-C of this example proceed substantially according to
the following scheme 6: 19
[0251] Part A: Synthesis of the Control Agent
[0252] 2-Bromopropionyl bromide 1 reacted with N-silyl protected
ethanolamine to form the corresponding amide. Subsequently
deprotection of silyl group occurred in acidic medium during the
workup to give the N-hydroxyethyl 2-bromoacrylamide 2 in a
quantitative yield. With no further purification, compound 2 was
coupled with sodium dithiocarbamate to yield a yellow solid
("Control agent") compound 3 in 75% yield. All compounds were
characterized by .sup.1H NMR.
[0253] Part B: Depolymerization of the Cellulosic Backbone
[0254] 50 g of cellulose triacetate ("CTA") (purchased from
Aldrich, with a degree of substitution of about 2.7) was dissolved
in 1000 ml of dichloroethane (purchased from Aldrich and used
without any further purification) under inert atmosphere and heated
to 70.degree. C. with vigorous stirring. To this solution 0.5 ml of
BF.sub.3. Et.sub.2O was added as a solution in 5 ml of
dichloromethane. The mixture was stirred at 70.degree. C. and the
reaction was monitored by gel permeation chromatography (GPC). When
the desired molecular weight was achieved (about 20,000 number
average molecular weight (M.sub.n)), the reaction was quenched with
triethylamine and allowed to cool to room temperature. The product
was isolated by precipitation into ethyl ether or methanol or
acetone or ethyl acetate. The product was purified by dissolution
in tetrahydrofuran (THF) and re-precipitation from ethyl ether. The
product was characterised by .sup.1H NMR and GPC.
[0255] Part C: Attachment of Control Agent to Cellulosic
Backbone
[0256] Attachment of control agent one end of the linker: 15 g of
the control agent (from part A, above) was suspended in 150 ml of
dry dichloromethane under an inert atmosphere. 50 ml of the
dichloromethane was distilled off and the mixture was cooled to
room temperature. 21 ml of hexane diisocyanate was added to the
reaction followed by 200 .mu.l of dibutyltin dilaurate. The
reaction was stirred at room temperature for 15 minutes. The
reaction mixture was then transferred into 1000 ml of dry hexane
using a cannula. This mixture was stirred for 10 minutes and
filtered. The residue was dissolved in dichloromethane and
re-precipitated. The residue was isolated by filtration and dried
under vacuum. This produces a control agent attached to one end of
the linker, referred to as "control agent-linker".
[0257] 20g of depolymerized cellulose triacetate (M.sub.n 20,000
from part B, above) was suspended in 100 ml of benzene. The mixture
was then distilled to dryness under atmospheric pressure to
azeotropically remove water from the cellulose triacetate. 100 ml,
of dry dichloromethane was added to the vessel and 50 ml was
removed by distillation. 2.5 g of the control agent-linker from the
previous paragraph was added to the reaction followed by 200 .mu.l
of dibutyl dilaurate. The mixture was then stirred at 40.degree. C.
for 12 hours. After this, the reaction mixture was cooled to room
temperature, diluted to 150 ml with dichloromethane and
precipitated by pouring into methanol. The residue was isolated by
filtration and purified by re-precipitation from THF into methanol.
The product was characterized by .sup.1H NMR and GPC.
[0258] Part D: Controlled Polymerisation of Vinyl Monomers onto the
Cellulosic Backbone
[0259] Polymerisation was carried out in a glove box with an inert
atmosphere. The control agent modified cellulosic backbone (from
part C) was dissolved in degassed dimethylformamide (DMF). To this,
the desired vinyl monomer or monomers were added followed by
azo-bis-isobutyronitrile (AIBN). The vial was then sealed and the
contents stirred at about 60.degree. C. for about 18 hours.
[0260] The following Table 1 describes the synthesis of 20 polymers
of dimethylacrylamide and/or acrylic acid grafted onto a cellulosic
backbone (M.sub.n about 20,000) modified with xanthate control
agent (with Z=-OEt (see Scheme 6 above)) and with about 5.7 control
agents per chain, as measured by NMR. Assuming a number average
molecular weight of about 20,000, these polymers have a degree of
substitution (DS) of about 0.057. The length of the grafts is
controlled by the weight ratio of monomer to cellulosic backbone.
The reactants are listed in milligrams and the reactions were
carried out in 1 ml vials in accord with the above described
procedure.
1TABLE 1 Cta- Dimethyl 20K-hdi-5.7-A Acrylic acid acrylamide AIBN
DMF 1 50 1.25 23.75 0.117 174.8805 2 50 6.25 18.75 0.117 174.8805 3
50 12.5 12.5 0.117 174.8805 4 50 18.75 6.25 0.117 174.8805 5 50
23.75 1.25 0.117 174.8805 6 50 2.5 47.5 0.117 233.213 7 50 12.5
37.5 0.117 233.213 8 50 25 25 0.117 233.213 9 50 37.5 12.5 0.117
233.213 10 50 47.5 2.5 0.117 233.213 11 25 2.5 47.5 0.0585 174.939
12 25 12.5 37.5 0.0585 174.939 13 25 25 25 0.0585 174.939 14 25
37.5 12.5 0.0585 174.939 15 25 47.5 2.5 0.0585 174.939 16 25 5 95
0.0585 291.604 17 25 25 75 0.0585 291.604 18 25 50 50 0.0585
291.604 19 25 75 25 0.0585 291.604 20 25 95 5 0.0585 291.604
[0261] At the end of the reaction, polymers were obtained in each
case and the mixtures were diluted to a concentration of about
16.6% polymer in DMF.
[0262] Part E: Saponification
[0263] Saponification of the cellulosic backbone is carried out by
starting with about 16.6% of polymer in DMF added into 0.25M NaOH
and stirred at 50.degree. C. This was stirred for 30 minutes and
thereafter cooled to room temperature.
[0264] B. Compositions and Their Use
Example 2
[0265] Demonstration of adsorption to cotton and effect of
architecture on the adsorbed amount. Eight samples of
polydimethylacrylamide grafted on cellulose monoacetate (CMA) were
prepared substantially according to the methods of Example 1. In
this example, the control agent was one where "Z" was pyrrole (see
scheme 6, above). The number of grafts and lengths were varied. A
small amount of a fluorescent monomer, having the structure 20
[0266] was incorporated in the grafts during polymerisation of the
dimethylacrylamide monomer.
[0267] The following conditions were employed:
[0268] Molecular weight of CMA (Mn).about.20,000
[0269] DS of control agent 0.075 and 0.15 onto the CMA
[0270] CMA: Monomer weight ratio varies from 1:2 to 1:16
[0271] Amount of fluorescent monomer: 0.75 mg in each sample
[0272] Total amount of polymer 150.75 mg
[0273] Total solids concentration: 33.33%
[0274] Amount of AIBN: 10 mole % compared to control agent.
[0275] Reaction temperature: 60.degree. C.
[0276] Reaction time: 18 hrs
[0277] Table 2 shows the amounts used in the polymerisation
mixtures. The grafts on the eight samples were polymerised in the
following ratios, where "CMA-DS-0.075" represents cellulose
monoacetate with a degree of substitution of 0.075 control agents
in the cellulosic backbone (a graft density of 6 grafts per
cellulosic backbone was measured by NMR) and "CMA-DS-0.15"
represents cellulose monoacetate with a degree of substitution of
0.15 control agent in the cellulosic backbone (a graft density of
12 grafts per cellulosic backbone was measured by NMR):
2 CMA-DS-0.15 CMA-DS.0.075 Dimethyl (mg) (mg) DMF (mg) acrylamide
(mg) 1 -- 50 350 100 2 -- 30 350 120 3 -- 16.67 350 133.33 4 --
8.82 350 141.18 5 50 -- 350 100 6 30 -- 350 120 7 16.67 -- 350
133.33 8 8.82 -- 350 141.18
[0278] Each polymerisation resulted in a cellulose monoacetate
graft polydimethylacrylamide polymer. The amount of
dimethylacrylamide in the polymerisation mixture determined the
graft length.
[0279] The polymers were diluted in two steps to achieve a
concentration of 200 ppm by weight in a buffered surfactant
solution. The composition of the surfactant solution is as follows,
with the solvent being demineralised water:
[0280] 0.6 g/L LAS anionic surfactant ((made from the reaction of
dodecylbenzene sulphonic acid (e.g., Petrelab 550 available from
Pretresa) and sodium hydroxide (e.g., available from Aldrich)
resulting in a ca. 50 wt. % (in water) solution of the sodium salt
of the acid, which is referred to as "LAS").
[0281] 0.4 g/L R(EO).sub.7
[0282] 1.25 g/L Na.sub.2CO.sub.3--JT Baker #3604-01
[0283] 1.1 g/L STP (sodium triphosphate, available from
Aldrich).
[0284] 1.0 g/L NaCl
[0285] 0.0882 g/L CaCl.sub.2 2H.sub.2O--Sigma #C-8106
[0286] pH=10.5.
[0287] The polymers were prepared at a nominal concentration of 30
wt % solids in DMF, and were used without any subsequent
purification to remove solvent, unreacted monomer, etc. In the
first dilution step, 66 .mu.l of each crude reaction mixture was
added to 2 ml of the surfactant solution, in a 2 ml capacity
96-well polypropylene microliter plate. This gave an initial
dilution of 1:30, or a polymer concentration of 1% w/v. The
solutions were mixed by repeated aspiration and dispensing from a
pipette into the well of the microtiter plate. In the second
dilution step, 40 .mu.l of the 1 % w/v solutions were added to 2 ml
of the surfactant solution in a second microtiter plate and mixed,
giving an additional factor of 50 dilution and a final
concentration of 0.02% w/v or 200 ppm w/v.
[0288] The polymers were tested for adsorption to cotton fabric
using an apparatus for simultaneously contacting different liquids
with different regions of a single sheet of fabric.
[0289] This apparatus is described in detail in U.S. patent
application Ser. No. 09/593,730, filed Jun. 13, 2000, which is
incorporated herein by reference. Briefly, six sheets of fabric
were clamped between an upper and lower block. The fabric sheets
had previously been printed with rubbery, cross-linked ink in
microtiter plate pattern using standard screen printing techniques
and materials. Both blocks contain 8.times.12 arrays of square
cavities, which are aligned with un-printed regions of the fabrics.
When the blocks and fabrics are clamped together, liquids placed in
the individual wells do not leak or bleed through to other wells,
due to the pressure applied by the blocks in the regions separating
the wells, and due to the presence of the cross linked ink in these
regions, which fills the pores between the fibres. The liquids are
forced to flow back and forth through the fabric by means of a
pneumatically actuated thin rubber membrane, which is placed
between the fabrics and the lower block. Repeated flexing of the
membrane away from and towards the fabrics results in fluid motion
through the fabrics.
[0290] Six white cotton fabrics were tested simultaneously in a
single washing apparatus. 400 .mu.l of the 200 ppm
polymer/surfactant solutions were placed in the corresponding wells
in the washing apparatus. The liquids were flowed through the
fabrics for 1 hour at room temperature, with a flow cycle time of
approximately 0.5 seconds per complete cycle. After one hour, the
free liquid in the cells was poured off, and the apparatus was
immersed briefly in tap water to further remove free polymer
solution. The blocks were then separated, and the fabrics were
removed, separated, and thoroughly rinsed in 6 litres of tap water.
The fabrics were allowed to air dry for 24 hours.
[0291] The amount of adsorbed polymer was determined by
fluorescence imaging. Fluorescence imaging was performed by
mounting the sample on a stage in a light-tight enclosure. Near-UV
excitation (.about.365 nm) was provided by a pair of 8 watt UV
fluorescent lamps mounted above and to the side of the sample on
adjustable mounts. The total irradiance incident upon the sample
was .about.1.8 mW/cm.sup.2 as measured with a calibrated radiometer
(Minolta UM-1w/UM-36 detector). Rejection of undesired reflected
light was performed with a glass bandpass filter (Oriel part #
59850) having a centre wavelength of 520 nm, maximum transmission
of 52%, and FWHM bandwidth of .about.90 nm, mounted directly in
front of the imaging lens. The photoluminescence of the samples was
collected with an imaging grade lens of 60 mm focal length (Micro
Nikkor) and imaged on a thermoelectrically cooled, 1152.times.1242
pixel, front illuminated, research grade focal plane array CCD
detector (available from Princeton Instruments) under computer
control. The exposure time was 20 seconds.
[0292] The images were analysed on a computer using a program which
allows the user to define a centroid position for the top left and
bottom right library element; centroids for the remaining elements
are then automatically generated using a simple gridding algorithm.
The user also manually defines the size of a rectangular area
around each centroid which is to be included In the analysis. Both
the total number of counts within the sampled area and the average
counts per pixel are calculated and stored, for each element in the
grid. The latter number is used for comparisons between libraries,
since the sampling area is set manually for each image and is not
constant from one library to the next.
[0293] To calibrate the relationship between the amount of adsorbed
polymer and the fluorescence signal, known amounts of the polymers
were deposited on a second piece of fabric. This was done by first
preparing a series of solutions at known polymer concentrations,
beginning with a 1% wt concentration and diluting progressively by
factors of two for a total of eight concentrations. This was done
for all eight poly(DMA-graft-CMA) polymers being tested, for a
total of 64 test solutions, 1 ml of each contained in an 8.times.8
array of cells in a 2 ml microtiter plate. For each solution, 5
.mu.l was pipetted directly onto the corresponding square of the
second fabric, and allowed to dry. The total amount of polymer
deposited can be calculated from the product of the solution
concentration times the volume deposited (Table 2, below). The
average mass of fabric in each square is 7.5 mg. The calibration
sample with deposited polymers was imaged in the fluorescence
system described above under identical conditions to the "test"
fabrics containing the adsorbed graft polymers.
[0294] The calibration results are shown in Table 2 and FIG. 3. The
fluorescence measurements for a given polymer concentration were
averaged over the eight different polymers tested, which all
contain approximately the same amount of fluorescent monomer per
mass of polymer.
3 Polymer Mg polymer Solution Volume mass One cotton deposited
Average Std. Error, mass deposited, deposited, square per gm counts
per from 8 fraction .mu.l mg mass cotton pixel samples 1.00E-02 5
5.00E-02 0.0075 6.67E+00 3.29E+04 1.90E+03 5.00E-03 5 2.50E-02
0.0075 3.33E+00 2.43E+04 5.13E+02 2.50E-03 5 1.25E-02 0.0075
1.67E+00 2.09E+04 3.70E+02 1.25E-03 5 6.25E-03 0.0075 8.33E0-01
1.95E+04 2.52E+02 6.25E-04 5 3.13E-03 0.0075 4.17E-01 1.81E+04
1.45E+02 3.13E-04 5 1.56E-03 0.0075 2.08E-01 1.73E+04 1.34E+02
1.56E-04 5 7.81E-04 0.0075 1.04E-01 1.74E+04 9.26E+01 7.81E-05 5
3.91E-04 0.0075 5.21E-02 1.70E+04 7.32E+01 0.00E+00 5 0.00E+00
0.0075 0.00E+00 1.68E+04 1.13E+02
[0295] Referring to FIG. 3, a straight line. was fitted to the
calibration data, yielding the relationship:
counts per pixel=a+b*(mg polymer/gram cotton)=1.7E+04+1.97E+03*(mg
polymer/gram cotton).
[0296] The parameter a gives the number of counts observed for
cotton squares carrying no dye, and contains contributions from the
dark current of the CCD, any intrinsic fluorescence from the undyed
fabric (including any chemicals used in manufacture and/or
processing of the fabric), and any of the UV excitation which
passes through the filter.
[0297] In practice the value of a was found to vary slightly from
one fabric array to the next and was determined for each fabric as
an average divided by (or "over") all cells not carrying any dye
(i.e., "blanks"). Thus for the test cells, to which the dye-tagged
graft polymers were allowed to adsorb from solution, the amount of
adsorbed polymer was determined from the averaged number of counts
per pixel as
mg polymer/gram cotton=(counts per pixel-a)/b
[0298] where the same slope value b-1970 was used for all samples,
but the value of the intercept a was determined from the blanks by
averaging for each 8.times.12 fabric array tested. The results of
processing this data are shown in FIG. 4 (in units of mg
polymer/gram cotton), averaged over all four fabrics tested, and
including error bars which represent the standard error calculated
from the four measurements. As FIG. 4. demonstrates, the amount of
adsorbed polymer decreases gradually as the length of the grafts is
increased over a wide range.
[0299] Separate experiments were done in order to demonstrate that
free dye in solution binds weakly or not at all to the cotton
fabric, and that poly(dimethylacrylamide) homopolymers containing
dye do not adsorb significantly to the cotton fabric.
Example 3
Effect of Graft Architecture on the Adsorbed Amount
[0300] A variety of different polymers were grafted from cellulose
monacetate (CMA), with different degrees of substitution of the
grafts and different degrees of polymerisation of the grafts. The
monomers used for the grafts were dimethylacrylamide (DMA),
trishydroxymethylmethylacry- lamide (THMMA), acrylamide
methylpropane sulphonic acid triethylamine salt (AMPS:Et3N) and
N-carboxymethyl dimethylaminopropyl acrylamide (N-carbDMAPA). The
graft chains were present in seven different degrees of
substitution across the bulk sample, namely DS of 0.012, 0.023,
0.04, 0.072, 0.125, 0.18 and 0.27. For each of the first 4 degrees
of substitution, five graft polymers were prepared with different
degrees of polymerisation (DP) of the grafts, with DP's of 25, 50,
100, 200 and 400 being targeted. For each of the last 3 degrees of
substitution, four graft polymers were prepared with different
degrees of polymerisation of the grafts, with DP's of 25, 50, 100
and 200 being targeted. The polymerisation proceeded substantially
according to the methods of Examples 1 and 2.
[0301] In this example, the control agent was one where "Z" was
pyrrole (see scheme 6 above). 0.5 mol % of a fluorescent monomer
(structure shown below) 21
[0302] was incorporated in all the grafts during polymerisation of
the grafts. CMA was used as a 20 wt % solution in DMF.
Dimethylacrylamide was used as a 50% solution in DMF.
Trishydroxymethylmethylacrylamide was used as a 20% solution in
DMF. Acrylamidomethylpropanesulfonic acid triethylamine salt was
used as a 20% solution in DMF.
N-Carboxymethyldimethylaminopropylacrylamide was used as a 20%
solution in water. AIBN was used as a solution in DMF.
[0303] The following procedure is representative for the synthesis
of all other polymers in this example: for CMA-DS-0.012 and monomer
DMA at a DP=25: in an inert N.sub.2 atmosphere CMA (89.21 mg) and
dimethylacrylamide (10.79 mg) were mixed in a vial. To this AIBN
(0.089 mg) was added and the mixture was heated to 65.degree. C.
and stirred for 18 hours. The reaction mixture was then diluted to
10 wt % with DMF.
[0304] Other than DMF, the following tables 4-10 provide the
amounts of reactants used in each polymerisation mixture.
4TABLE 4 DS DP CMA-Pyrrole-0.012 AIBN DMA THMMA AMPS:Et3N
N-CarbDMAPA 0.012 25 89.21 0.089 10.79 0 0 0 0.012 50 80.53 0.161
19.47 0 0 0 0.012 100 67.41 0.27 32.59 0 0 0 0.012 200 50.84 0.407
49.16 0 0 0 0.012 400 34.08 0.546 65.92 0 0 0 0.012 25 82.41 0.083
0 17.59 0 0 0.012 50 70.09 0.14 0 29.91 0 0 0.012 100 53.95 0.216 0
46.05 0 0 0.012 200 36.94 0.296 0 63.06 0 0 0.012 400 22.65 0.363 0
77.35 0 0 0.012 25 72.7 0.073 0 0 27.3 0 0.012 50 57.1 0.114 0 0
42.9 0 0.012 100 39.96 0.16 0 0 60.04 0 0.012 200 24.97 0.2 0 0
75.03 0 0.012 400 14.27 0.229 0 0 85.73 0 0.012 25 80.31 0.08 0 0 0
19.69 0.012 50 67.1 0.134 0 0 0 32.9 0.012 100 50.49 0.202 0 0 0
49.51 0.012 200 33.77 0.271 0 0 0 66.23 0.012 400 20.32 0.325 0 0 0
79.68
[0305]
5TABLE 5 DS DP CMA-Pyrrole-0.023 AIBN DMA THMMA N-carbDMAPA
AMPS:Et3N 0.023 25 80.9 0.158 19.1 0 0 0 0.023 50 67.93 0.266 32.07
0 0 0 0.023 100 51.44 0.402 48.56 0 0 0 0.023 200 34.62 0.541 65.38
0 0 0 0.023 400 20.94 0.655 79.06 0 0 0 0.023 25 70.59 0.138 0
29.41 0 0 0.023 50 54.55 0.213 0 45.45 0 0 0.023 100 37.5 0.293 0
62.5 0 0 0.023 200 23.08 0.361 0 76.92 0 0 0.023 400 13.04 0.408 0
86.96 0 0 0.023 25 57.7 0.113 0 0 0 42.31 0.023 50 40.54 0.159 0 0
0 59.46 0.023 100 25.42 0.199 0 0 0 74.58 0.023 200 14.56 0.228 0 0
0 85.44 0.023 400 7.85 0.246 0 0 0 92.15 0.023 25 67.63 0.132 0 0
32.37 0 0.023 50 51.09 0.2 0 0 48.91 0 0.023 100 34.31 0.268 0 0
65.69 0 0.023 200 20.71 0.324 0 0 79.29 0 0.023 400 11.55 0.361 0 0
88.45 0
[0306]
6TABLE 6 DS DP CMA-Pyrrole-0.04 AIBN DMA THMMA AMPS:Et3N
N-carbDMAPA 0.04 25 68.64 0.261 31.48 0 0 0 0.04 50 52.14 0.396
47.86 0 0 0 0.04 100 35.26 0.536 64.74 0 0 0 0.04 200 21.41 0.651
78.59 0 0 0 0.04 400 11.99 0.729 88.01 0 0 0 0.04 25 55.24 0.21 0
44.76 0 0 0.04 50 38.16 0.29 0 61.84 0 0 0.04 100 23.58 0.359 0
76.42 0 0 0.04 200 13.37 0.406 0 86.63 0 0 0.04 400 7.16 0.436 0
92.84 0 0 0.04 25 41.22 0.157 0 0 58.78 0 0.04 50 25.96 0.197 0 0
74.04 0 0.04 100 14.92 0.227 0 0 85.08 0 0.04 200 8.06 0.245 0 0
91.94 0 0.04 400 4.2 0.255 0 0 95.8 0 0.04 25 51.8 0.197 0 0 0 48.2
0.04 50 34.95 0.266 0 0 0 65.05 0.04 100 21.18 0.322 0 0 0 78.82
0.04 200 11.84 0.36 0 0 0 88.16 0.04 400 6.29 0.383 0 0 0 93.71
[0307]
7TABLE 7 DS DP CMA-Pyrrole-0.072 AIBN DMA THMMA N-carbDMAPA
AMPS:Et3N 0.072 25 56.79 0.358 43.21 0 0 0 0.072 50 39.66 0.5 60.34
0 0 0 0.072 100 24.73 0.623 75.27 0 0 0 0.072 200 14.11 0.711 85.89
0 0 0 0.072 400 7.59 0.765 92.41 0 0 0 0.072 25 42.68 0.269 0 57.32
0 0 0.072 50 27.13 0.342 0 72.87 0 0 0.072 100 15.69 0.396 0 84.31
0 0 0.072 200 8.514 0.429 0 91.49 0 0 0.072 400 4.45 0.448 0 95.55
0 0 0.072 25 29.73 0.187 0 0 0 70.27 0.072 50 17.46 0.22 0 0 0
82.54 0.072 100 9.56 0.241 0 0 0 90.44 0.072 200 5.02 0.253 0 0 0
94.98 0.072 400 2.58 0.26 0 0 0 97.42 0.072 25 39.33 0.248 0 0
60.67 0 0.072 50 24.48 0.309 0 0 75.52 0 0.072 100 13.94 0.352 0 0
86.06 0 0.072 200 7.5 0.378 0 0 92.5 0 0.072 400 3.89 0.393 0 0
96.11 0
[0308]
8TABLE 8 DS DP CMA-Pyrrole-0.125 AIBN DMA THMMA N-carbDMAPA
AMPS:Et3N 0.125 25 43.69 0.466 56.31 0 0 0 0.125 50 27.95 0.597
72.05 0 0 0 0.125 100 16.25 0.694 83.75 0 0 0 0.125 200 8.84 0.755
91.16 0 0 0 0.125 25 30.53 0.326 0 69.47 0 0 0.125 50 18.02 0.385 0
81.98 0 0 0.125 100 9.9 0.423 0 90.1 0 0 0.125 200 5.21 0.445 0
94.79 0 0 0.125 25 19.98 0.213 0 0 0 80.02 0.125 50 11.1 0.237 0 0
0 88.9 0.125 100 5.88 0.251 0 0 0 94.12 0.125 200 3.03 0.259 0 0 0
96.97 0.125 25 27.68 0.295 0 0 72.32 0 0.125 50 16.06 0.343 0 0
83.94 0 0.125 100 8.73 0.373 0 0 91.27 0 0.125 200 4.57 0.39 0 0
95.43 0
[0309]
9TABLE 9 DS DP CMA-Pyrrole-0.18 AIBN DMA THMMA N-carbDMAPA
AMPS:Et3N 0.18 25 38.56 0.509 61.44 0 0 0 0.18 50 23.89 0.63 76.11
0 0 0 0.18 100 13.56 0.716 86.44 0 0 0 0.18 200 7.28 0.768 92.72 0
0 0 0.18 25 26.23 0.346 0 73.77 0 0 0.18 50 15.09 0.398 0 84.91 0 0
0.18 100 8.16 0.431 0 91.84 0 0 0.18 200 4.26 0.449 0 95.74 0 0
0.18 25 16.81 0.222 0 0 0 83.19 0.18 50 9.17 0.242 0 0 0 90.83 0.18
100 4.81 0.254 0 0 0 95.19 0.18 200 2.46 0.26 0 0 0 97.54 0.18 25
23.64 0.312 0 0 76.36 0 0.18 50 13.4 0.354 0 0 86.6 0 0.18 100 7.18
0.379 0 0 92.82 0 0.18 200 3.73 0.393 0 0 96.27 0
[0310]
10TABLE 10 DS DP CMA-Pyrrole-0.27 AIBN DMA THMMA N-carbDMAPA
AMPS:Et3N 0.27 25 32.35 0.56 67.65 0 0 0 0.27 50 19.3 0.668 80.7 0
0 0 0.27 100 10.68 0.74 89.32 0 0 0 0.27 200 5.64 0.782 94.36 0 0 0
0.27 25 21.32 0.369 0 78.68 0 0 0.27 50 11.93 0.413 0 88.07 0 0
0.27 100 6.34 0.439 0 93.66 0 0 0.27 200 3.28 0.454 0 96.72 0 0
0.27 25 13.34 0.231 0 0 0 86.66 0.27 50 7.15 0.248 0 0 0 92.85 0.27
100 3.71 0.257 0 0 0 96.29 0.27 200 1.89 0.262 0 0 0 98.11 0.27 25
19.08 0.331 0 0 80.92 0 0.27 50 10.55 0.365 0 0 89.45 0 0.27 100
5.57 0.386 0 0 94.43 0 0.27 200 2.86 0.397 0 0 97.14 0
[0311] Conversions were spot checked by NMR for selected samples
and graft polymers of DMA and TRIS were analysed by aqueous GPC.
The DS for grafts across the bulk sample were measured by NMR
according to the discussion in this specification. Each
polymerisation resulted in a cellulose monoacetate graft polymer.
The amount of monomer in the polymerisation mixture determined the
graft length.
[0312] Using the parallel deposition contacting apparatus and
method described in Example 2, after synthesis, the reaction
mixtures were topped off with solvent to bring the total polymer
concentration to a nominal value of 12.5 wt % in all wells (100 mg
polymer in 800 .mu.l solvent). These solutions were used without
any subsequent purification to remove solvent, unreacted monomer,
etc. The polymers were diluted in two steps to achieve an ultimate
concentration of 200 ppm by weight in a buffered surfactant
solution. The composition of the surfactant solution is as follows,
with the solvent being demineralised water:
[0313] 0.6 g/L LAS anionic surfactant ((made from the reaction of
dodecylbenzene sulphonic acid (e.g., Petrelab 550 available from
Pretresa) and sodium hydroxide (e.g., available from Aldrich)
resulting in a ca. 50 wt. % (in water) solution of the sodium salt
of the acid, which is referred to as "LAS").
[0314] 0.4 g/L R(EO).sub.7
[0315] 1.25 g/L Na.sub.2CO.sub.3--J T Baker #3604-01
[0316] 1.1 g/L STP (sodium triphosphate, available from
Aldrich).
[0317] 1.0 g/L NaCl
[0318] 0.0882 g/L CaCl.sub.2 2H.sub.2O--Sigma #C-8106
[0319] pH=10.5.
[0320] In the first dilution step, 32 .mu.l of each polymer
solution was added to 2 ml of the surfactant solution, in a 2 ml
capacity 96-well polypropylene microtiter plate. This gave an
initial dilution of 1:62.5, for a polymer concentration of 0.2 wt
%. The solutions were mixed by multi-well magnetic stirring. In the
second dilution step, 40 .mu.l of the 0.2 wt % solutions and 360
.mu.l of the surfactant solution were added together directly in
the apparatus used for screening adsorption in parallel format
(described in Example 2). The final polymer concentration is thus a
nominal 0.02 wt % or 200 ppm by weight.
[0321] The liquids (sample/surfactant solutions) were flowed
through the fabrics for 1 hour at room temperature, with a flow
cycle time of approximately 0.5 seconds per complete cycle. After
one hour, the free liquid in the cells was poured off, and the
apparatus was immersed briefly in tap water to further remove free
polymer solution. The blocks were then separated, and the fabrics
were removed, separated, and thoroughly rinsed in 6 litres of tap
water. The fabrics were allowed to air dry for 24 hours.
[0322] Each square of the rest fabrics has a mass of approximately
7.5 mg, so the total fabric mass per well is approximately 45 mg.
The mass of sample/surfactant solution in each well is
approximately 400 mg (400 .mu.l volume), containing a polymer mass
fraction of 0.02% or a polymer mass of 0.08 mg. Thus the maximum
amount of polymer which can be deposited on the fabric is 0.08
mg/45 mg=1.8 mg polymer per gram of fabric. In order to calculate
from the fluorescence signals the amount of polymer actually
deposited from the wash, additional fabrics were prepared by
directly depositing controlled amounts of the polymers on squares
of the test fabrics. The solutions at 0./2 wt % polymer were used
for this purpose. A volume of approximately 3.5 .mu.l of each
solution was deposited, carrying a total polymer mass of 0.007 mg
and giving polymer deposition relative to the fabric in the amount
(0.007 mg polymer per square)/(7.5 mg fabric per square)=0.9 mg/gm.
This is one half the maximum possible amount of polymer that could
be deposited under the test conditions.
[0323] The amount of deposited polymer was determined by
fluorescence imaging as described in Example 2, but in this
example, the f-stop value was f4 and the exposure time was 500
msec. A background image was obtained by taking an exposure with
the UV illumination turned off. The effects of non-uniform UV
illumination were accounted for by imaging a uniform fluorescent
target (Peel-N-Stick Glow Sheeting, manufactured by ExtremeGlow,
http://www.extremeglow.com) under the same irradiation and exposure
conditions used for imaging the fabrics. The number of counts in a
pixel in an experiment image was corrected by first subtracting the
number of counts in the corresponding background image pixel, and
then dividing by the number of counts in the corresponding uniform
target pixel.
[0324] The corrected images were analysed on a computer using a
program that allows the user to define a centroid position for the
top left and bottom right library element. Centroids for the
remaining elements are then automatically generated using a simple
gridding algorithm. The user also manually defines the size of a
circular area around each centroid which is to be included in the
analysis. Both the total number of counts within the sampled area
and the average counts per pixel are calculated and stored, for
each element in the grid. The latter number is used for comparisons
between libraries, since the sampling area is set manually and is
not necessarily constant from one library to the next. See, for
example, WO 00/60529 for disclosure of such a program, which is
incorporated herein by reference.
[0325] FIG. 5 shows a subset of the data, where DS is equal to
0.023 (FIG. 5A) and 0.18 (FIG. 5B). The lower points in each plot
represent the signal from the experimental samples, and the upper
points (shown as triangles ".tangle-solidup.") represent twice the
signal from the control samples, i.e., the signal which would occur
if all polymer were deposited. The upper points thus represent the
amount of graft available in solution, and the lower points
represent the amount of graft actually deposited on the fabric from
the deposition step. From FIG. 5A, the amount of deposited grafted
polymer reaches a maximum at about DP=100 and then decreases, even
though the amount of graft available for deposition continues to
increase. From FIG. 5B, the amount of deposited graft polymer is
much less than for DS=0.023, even though the amount of available
graft is in all cases larger. Also the amount of deposited polymer
essentially decreases monotonically with increasing DP, even though
the amount of available graft is increasing monotonically. Similar
data was obtained for the other tested graft polymers in this
example, for example for dimethylacrylamide grafts, with DS values
of 0.012 and 0.125, the trends of available vs. adsorbed polymer
were'similar to those observed for THMMA grafts.
[0326] FIG. 6 summarises the results for all of the polymers with
THMMA grafts. The x-axis is the number of grafts per chain
(=DS*100) and the y-axis is the targeted graft degree of
polymerisation, DP. The size of the data points is proportional to
twice the signal from the "control" sample, and the relative shade
of the data points represents the fluorescence signal from the
experimental samples. The size of the points increases
monotonically with both DP and DS, because the graft makes up a
larger fraction of the polymer as each of these variables
increases. The region where the point interiors are lighter
represents the region in which the deposition of the grafts is
optimised or maximised. An oval has been drawn in FIG. 6 around the
region where an anti-correlation exists between the optimum values
of DS and DP--as DS is increased, the value of DP which gives
optimum deposition decreases, which represents the approximate
region where strong deposition occurs.
Example 4
Clothes Care
[0327] Materials
[0328] Materials were synthesised from CMA modified with the
pyrrole control agent
11 control DP of Code graft material agent DS grafts Mw Mn DMA50
dimethylacrylamide 0.072 50 27000 13000 DMA200 dimethylacrylamide
0.025 200 39000 22000 TRIS50 trishyhdroxymethylacrylamide 0.072 50
21000 12000 TRIS200 trishydroxymethylacrylamide 0.025 200 26000
16000 AMMPS50 acrylamidomethylpropanesulphonic 0.072 50 acid:
triethylamine salt AMMPS200 acrylamidomethylpropanesulphonic acid:
0.025 200 triethylamine salt Zwitter50
N-carboxymethyldimethylaminopropaneacrylamide 0.072 50 Zwitter200
N-carboxymethyldimethylaminopropaneacrylamide 0.025 200 DMA =
dimethylacrylamide TRIS = tris-hydroxymethylmethylacrylamid- e
AMMPS = acrylamidomethylpropanesulfonic acid (triethylamine salt)
Zwitter = N-carboxymethyldimethylaminopropaneacrylamide
[0329] 1. Test Protocols
[0330] Linitester DTI Method
[0331] 6 Linitester pots were filled with the following reagents
and cloths:
12 Pot 2-5 Pot 1 4 different Pot 6 CMA polysaccharides Control
Demineralised water 160 mls 160 mls 160 mls 10 g/l surfactant 20
mls 20 mls 20 mls stock (LAS:A7/50:50) 0.1 M buffer stock 20 mls 20
mls 20 mls White Cotton Monitor .about.5.77 g .about.5.77 g
.about.5.77 g (20 .times. 20 cm (5.77 g)) Direct Red Cloth
.about.5.77 g .about.5.77 g .about.5.77 g (1% dyed no fixer) (20
.times. 20 cm) 0.4 g/l CMA 0.08 g N/A N/A 0.4 g/l experimental N/A
0.08 g N/A polysaccharides Total liquor volume 200 mls 200 mls 200
mls Liquor to cloth ratio 17:1
[0332] The white cotton cloth was desized, mercerised, bleached,
non-fluorescent cotton prepared via method 1.20 in Docfind. The
direct red 80 was 1% dyed from stock.
[0333] The 0.1M buffer stock contained 0.08 M Na.sub.2CO.sub.3+0.02
M NaHCO.sub.3. This gives pH.apprxeq.10.5-10.0 at 0.01M in the
final liquor. The surfactant stock contained 50:50 wt % LAS:
Synperonic A7. The surfactant stock delivers 1 g/l total surfactant
in the final liquor.
[0334] All the experiment's liquors were added to their respective
containers except for the cloths and the polysaccharide samples.
Next the cloths and the polysaccharides were added to their
respective containers and the wash run for 30 minutes in the
Linitester set at 40.degree. C. and 40 rpm. After 30 minutes a
sample of the liquor was removed from the containers and stored in
glass vials. In total there were 6 pots (1 control, 1 with
unmodified CMA for comparison and 4 modified polysaccharides). The
cloths were then removed; rinsed in demineralised water twice and
then line dried for 30 minutes.
[0335] This procedure was repeated 4 more times to give results
over 5 washes. After 5 washes the cloths were ironed and then
stored in the humidity controlled room at 20.degree. C. and 65%
humidity for 24 hours. This ensured a degree of control over the
moisture within the samples.
[0336] Colour Analysis (Colour Fading & Dye Transfer
Inhibition)
[0337] The reflectance spectrum of the cloths were measured after
each wash cycle, using the ICS Texicon Spectraflash. Settings were
UV excluded from 420 nm, Specular included, Large aperture, 4 cloth
thickness. Readings were also taken from a non-treated piece of the
same fabrics (Direct Red and white) to compare against. The
reflectance spectra were used to calculate CIELAB)E and % colour
strength values for the white and red cloths respectively.
[0338] Kawabata Suite Shear Hysterisis (Softness/Anti-Wrinkle)
[0339] Fabric was measured according to the standard instruction
manual for this instrument. Testing was performed with the warp
direction perpendicular to the motion of the clamping bars. The
instrument outputted the measurements as average values of two
replicates with the figures for 2HG5, (Hysteresis at 5.degree. of
shear). Those skilled in the art will know that the 2HG5 value is a
good predictor of softness and anti-wrinkle properties of the
fabric.
[0340] Crease Recovery Angle (CRA) (Anti-Wrinkle Benefit)
[0341] Measurements were performed using the "Shirley" Crease
Recovery Angle apparatus (U.S. Pat. No. 1,554,803) with six
replicates for each treatment according to BS:EN 22313:1992. Fabric
was tested only in the warp direction on pieces 5.times.2.5 cm. All
pieces were handled using tweezers to ensure no contamination.
Results are reported as the average of the measurements.
[0342] Residual Extension (Dimensional Stability)
[0343] The residual extension was determined using an Instron
Testometric (trade mark) tester:
13 Sample size: 150 mm .times. 50 mm Clamp width: 25 mm Stretch
area: 100 mm .times. 25 mm Elongation rate: 100 mm/min Extension
cycle: Begin at rest with 0 kg force Extend until 0.2 kg force is
attained Return to 0 kg force
[0344] 2. Experimental Results
[0345] Key
14 + significant benefit - significant negative = statistically
indistinguishable
[0346] Anti-Wrinkle Benefit
15 Performance Compared to Treatment Crease recovery angle no
treatment unmodified CMA Control50 65.8 n/a n/a Control200 70.7 n/a
n/a CMA50 64.3 = n/a CMA200 71.2 = n/a DMA 50 73.2 + + DMA200 68.0
- - TRIS50 76.8 + + TRIS200 70.0 = = AMMPS50 71.7 = + AMMPS200 69.7
= = Zwitter50 70.8 + + Zwitter200 69.7 - =
[0347] Colour Fading
16 Performance Compared to % colour no unmodified Treatment
strength treatment CMA Control50 83.1 n/a n/a Control200 77.0 n/a
n/a CMA50 86.8 = n/a CMA200 83.7 + n/a DMA 50 79.9 = - DMA200 77.9
= = TRIS50 80.1 = - TRIS200 80.0 = = AMMPS50 81.9 = = AMMPS200 80.0
= = Zwitter50 80.0 + - Zwitter200 80.0 - =
[0348] Dye Transfer Inhibition
17 Performance Compared to Treatment Delta E no treatment
unmodified CMA Control50 44.8 n/a n/a Control200 45.5 n/a n/a CMA50
33.8 + n/a CMA200 34.6 + n/a DMA 50 34.3 + = DMA200 37.8 + - TRIS50
37.0 + - TRIS200 40.0 + - AMMPS50 43.6 = - AMMPS200 44.2 = -
Zwitter50 38.2 + - Zwitter200 41.9 + -
[0349] Softness/Anti-Wrinkle
18 Performance Compared to Treatment 2HE5 no treatment unmodified
CMA Control50 6.35 n/a n/a Control200 7.37 n/a n/a CMA50 7.17 - n/a
CMA200 7.27 = n/a DMA 50 6.49 = = DMA200 7.45 = + TRIS50 6.66 = =
TRIS200 6.67 + + AMMPS50 6.87 = = AMMPS200 7.73 = = Zwitter50 6.43
= + Zwitter200 7.42 = =
[0350] Dimensional Stability
19 Residual Performance Compared to Treatment Extension no
treatment unmodified CMA Control50 3.41 n/a n/a Control200 3.40 n/a
n/a CMA50 3.55 = n/a CMA200 3.40 = n/a DMA 50 3.27 = = DMA200 3.54
= = TRIS50 3.55 = + TRIS200 3.01 = = AMMPS50 3.94 = = AMMPS200 3.27
= = Zwitter50 2.93 + + Zwitter200 3.18 = =
Example 5
Soil Release
[0351] 1. Test Protocol
[0352] Conditions: Tergotometer, 100 rpm, 23.degree. C.
[0353] PRE-WASH: 6 3".times.3" desized cotton squares, in 1 litre
of wash liquor (liquor: cloth ca. 200:1)
[0354] wash liquor: 1 litre of wash liquour contains 0.6 g/l LAS,
0.75 g/l Na2CO3, 0.6 g/l NaCl, 0.66 g/l STP, made up in
demineralised water.
[0355] agitated for 20 mins
[0356] wash liquor decanted off
[0357] Rinse: 1 litre of demineralised water.
[0358] Agitated for 5 mins
[0359] Liquor decanted off, cloths removed and placed on racks to
dry
[0360] NB: cloths NOT wrung.
[0361] Before staining, cloths are reflected using GretagMacbeth
Coloreye
[0362] STAINING: Dirty motor oil (DMO) diluted to 15 wt. % in
toluene.
[0363] 0.1 ml of stain applied by pipette to each
[0364] 3".times.3" square. These were then left to dry on racks in
an oven (40.degree. C.) for 1 hour
[0365] After staining, cloths are reflected using GretagMacbeth
Coloreye
[0366] MAIN WASH & rinse: as pre-wash except no polymer was
present.
[0367] After washing, cloths are dried and reflected using
GretagMacbeth Coloreye.
[0368] ANALYSIS: results are obtained by extracting R460 values of
the cloths
[0369] 1. before staining (R.sub.clean)
[0370] 2. after staining (R.sub.stain)
[0371] 3. after final washing (R.sub.washed)
[0372] delta (.DELTA.) R is calculated for all samples including
control (no polymer treatment):
R.sub.washed-R.sub.stain
[0373] .DELTA..DELTA.R is then calculated for quick comparison to
the control
.DELTA.R.sub.polymer-.DELTA.R.sub.control
[0374] 2. Experimental Results
20 cloth .DELTA.R (washed-soiled) .DELTA..DELTA.R 1 control 15.5 --
2 AMMPS 50 16.2 0.7 3 TRIS 50 16.7 1.2 4 Zwitter 50 17.1 1.6 Key:
AMMPS 50 = CMA grafted with Acrylamidomethylpropanesulphonic acid
(triethylamine salt), graft DP = 50, TRIS 50 = CMA grafted with
Tris-hydroxymethylmethylacrylamide (Mw 21k, Mn 12k), graft DP = 50,
Zwitter 50 = CMA grafted with
N-carboxymethylDimethylaminopropaneacryla- mide, graft DP = 50,
[0375] It is to be understood that the above description is
intended to be illustrative and not restrictive. Many embodiments
will be apparent to those of skill in the art upon reading the
above description. The scope of the invention should, therefore, be
determined not with reference to the above description, but should
instead be determined with reference to the appended claims, along
with the full scope of equivalents to which such claims are
entitled. The disclosures of all articles and references, including
patent applications and publications, are incorporated herein by
reference for all purposes.
* * * * *
References